Reforming/dehydrocyclization catalysts

ABSTRACT

Reforming is effected with a combination of a primary supported noble-metal catalyst and a catalyst containing one or more medium-pore non-zeolitic molecular sieves (MP-NZMS). The latter reforming and dehydrocyclization catalysts comprise a Group VIII metal and at least one bound MP-NZMS characterized in the calcined form by an adsorption of isobutane of at least 2 percent by weight at a partial pressure of 500 torr and a temperature of 20° C. and characterized by an adsorption of triethylamine less than about 5 percent by weight at a partial pressure of 2.6 torr and a temperature of 22° C. The MP-NZMS catalyst binder preferably is alumina and/or silica, and the Group VIII metal preferably is platinum.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. Ser. No. 08/305,529, filed Sep.13, 1994, which is a continuation-in-part of prior application Ser. No.08/086,961 filed Jul. 2, 1993 now U.S. Pat. No. 5,346,611, which is acontinuation-in-part of Ser. No. 07/855,301, filed Mar. 23, 1922 nowU.S. Pat. No. 5,225,071, which is a continuation-in-part of Ser. No.07/625,273, filed Dec. 10, 1990, now U.S. Pat. No. 5,098,877, which is acontinuation-in-part of Ser. No. 07/447,340, filed Jan. 18, 1990,abandoned, which is a continuation of Serial No. 07/157,977, filed Feb.19, 1988abandoned, which is a division of Ser. No. 06/844,951, filedMar. 27, 1986, now U.S. Pat. No. 4,741,820.

FIELD OF THE INVENTION

The instant invention relates to reforming and dehydrocyclizationcatalysts and to processes employing such catalysts. The catalystscontain novel non-zeolitic molecular sieves, as hereinafter described.

BACKGROUND OF THE INVENTION

Reforming is a process generally known to the petroleum industry as aprocess for the treatment of naphtha fractions of petroleum distillatesto improve their octane rating by producing aromatic components fromcomponents present in the naphtha feedstock. Reforming is a complexprocess and involves a number of competing processes or reactionsequences. These include dehydrogenation of cyclohexanes to aromatics,dehydroisomerization of alkylcyclopentanes to aromatics,dehydrocyclization of an acyclic hydrocarbon to aromatics, andhydrocracking of paraffins to light products boiling outside thegasoline range. In addition, the dealkylation of alkylbenzenes and theisomerization of paraffins occur in reforming processes. Some of thereactions occurring during reforming are not desirable owing to theirdeleterious effect on the yield of commercially valuable products orupon the octane of the products. For example, hydrocracking reactionsproduce light paraffin gases, e.g., C₁ -C₄, and reduce the yield ofproducts boiling in the gasoline range.

The interest in catalytic reforming processes is fueled by a desire toimprove the production (yield) of the gasoline fraction whileconcurrently increasing its octane, while also having sufficientcatalytic activity to minimize the use of excessive temperatureconditions for the dehydrocyclization process.

Several catalysts have been generally employed for catalytic reforming.Catalysts comprising platinum on chlorinated-alumina supports and Pt--Xon alumina or chlorinated-alumina supports, where X is rhenium, iridiumor tin, have been used for reforming naphthas. U.S. Pat. No. 4,370,224discloses a multimetallic reforming catalyst comprised of platinum,iridium, copper, selenium and halogen, composited with an inorganicoxide support or carrier, preferably alumina. In addition, severalpatents have been issued for catalysts and/or processes employingzeolite-containing reforming catalysts. For example, several patentshave disclosed the use of the zeolite mordenite in reforming catalysts,e.g., see U.S. Pat. Nos. 3,546,102; 3,679,575; 4,018,711 and 3,574,092.In addition, the use of ZSM-type zeolites in reforming catalysts and/orprocesses have been disclosed in U.S. Pat. Nos. 4,104,320; 4,417,083;4,434,311 and 4,347,394. Further, the use of various forms of zeolite Lis disclosed in U.S. Pat. Nos. 4,104,320, 4,447,316, 4,347,394 and4,434,311. U.S. Pat. No. 4,417,083 discloses a process for theproduction of aromatic hydrocarbons in the presence of a two-bed processconfiguration employing a catalyst containing from 0.1 to 1.5% by weightof at least one metal selected from the group consisting of platinum,rhenium, iridium, tin and germanium, and containing sulfur in an atomicsulfur/metals ratio of from 0 to less than 1, supported on acrystalline, zeolitic aluminosilicate compensated by alkali metalcations, having a pore dimension larger than 6.5 Angstroms. The zeolitecomponent is employed as a carrier. Among the zeolites that can be usedare the Faujasites X and Y, the zeolite L and the zeolite omega.

Several chemical reactions occur during reforming. The most difficult ofthe desired reactions in reforming is the dehydrocyclization ofparaffins and may be employed to evaluate a catalyst for its usefulnessin reforming. The dehydrocyclization of paraffins containing six carbonatoms is one reaction carried out in reforming and is known to berelatively difficult. The ease of paraffin dehydrocyclization is knownto generally increase with the number of carbon atoms present in theparaffin. Accordingly, an acidic reforming catalyst useful in formingaromatics from C₆ paraffins would also be considered to be equal or moreeffective in the conversion of paraffins containing seven or more carbonatoms. This conversion of acyclic hydrocarbons to cyclized anddehydrogenated aromatic products produces valuable aromatic productshaving higher octane value than the paraffins from which they wereformed. Thus, the octane of the gasoline fraction increases as a resultof both the decrease in paraffins and as a result of the increase in thehigher octane value aromatic products with minimum yield loss ascompared with simple paraffin cracking.

Although the prior art catalysts for reforming and dehydrocyclizationhave included the use of Group VIII metals with chlorinated-alumina and,in some instances, selected zeolite materials, the prior art hasgenerally not disclosed the use of molecular sieves as components withnoble metal/chlorinated-alumina catalysts and has not disclosed the useof non-zeolitic molecular sieves as components inreforming/dehydrocyclization catalysts.

U.S. Pat. No. 4,440,871 discloses a class of crystallinesilicoaluminophosphates denominated as "SAPOs". The SAPOs of U.S. Pat.No. 4,440,871 are disclosed to be useful for hydrocarbon conversionreactions, including reforming and dehydrocyclization. The discussion ofthe use of SAPOs in reforming is set forth at column 70, lines 39 to 46and reads as follows:

"The SAPO catalyst compositions employed in hydrocracking are alsosuitable for use in reforming processes in which the hydrocarbonfeedstocks contact the catalyst at temperatures of from about 700° F. to1,000° F., hydrogen pressures of from 100 to 500 psig, LHSV values inthe range of 0.1 to 10 and hydrogen to hydrocarbon molar ratios in therange of 1 to 20, preferably between 4 and 12."

The discussion of the use of SAPOs in dehydrocyclization is set forth atcolumn 71, lines 25 to 32, and reads as follows:

"Dehydrocyclization reactions employing paraffinic hydrocarbonfeedstocks, preferably normal paraffins having more than 6 carbon atoms,to form benzene, xylenes, toluene and the like are carried out usingessentially the same reaction conditions as for catalyst cracking. Forthese reactions it is preferred to use the SAPO catalyst in conjunctionwith a Group VII non-noble metal cation such as cobalt and nickel."

The above disclosures generally refer to the use of the class of SAPOsof U.S. Pat. No. 4,440,871 as catalysts for reforming anddehydrocyclization. This general disclosure is supported by evaluationof representative SAPO samples for their first-order rate constant. Thefirst-order rate constant (k_(A)) is derived from a n-butane crackingexperiment described at column 72, line 63 to column 73, line 30. Thevalues for the first-order rate constants for SAPOs are set forth atcolumn 73, lines 21 to 30. SAPO-5 is reported to have a k_(A) of 1.4 and7.4 for two preparative examples, SAPO-11 is reported to have a k_(A) of0.5 and SAPO-31 is reported to have a k_(A) of 0.2. The meaning of therelative values of the first-order rate constants and their relationshipto hydrocarbon conversion processes is not discussed. Further, U.S. Pat.No. 4,440,871 does not discuss the selection of SAPOs for thehydrocarbon conversion processes.

The instant invention relates to novel reforming and dehydrocyclizationcatalysts and processes wherein the catalyst is formulated usingselected non-zeolitic molecular sieves, e.g., such as thesilicoaluminophosphates disclosed in U.S. Pat. No. 4,440,871, ascomponents in reforming catalysts.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts the relationship between the ratio of iso-C₆ s/lights inthe products as a function of the n-hexane conversion for examples 2 to10.

FIG. 2 depicts the relationship between the ratio of benzene/lights inthe products as a function of the n-hexane conversion for examples 2 to10.

FIG. 3 depicts the relationship between the calculated Volume % Yieldand the calculated Research Octane Number (RON) for the products ofexamples 2 to 9.

FIG. 4 depicts the relationship between the calculated Volume % Yieldand the calculated Research Octane Number (RON) for the products ofexamples 2 to 10.

FIG. 5 is a ternary diagram showing the compositional parameters of thesilicoaluminophosphates of U.S. Pat. No. 4,440,871 in terms of molefractions of silicon, aluminum and phosphorus.

FIG. 6 is a ternary diagram showing the preferred compositionalparameters of the silicoaluminophosphates of U.S. Pat. No. 4,440,871 interms of mole fractions of silicon, aluminum and phosphorus.

DESCRIPTION OF THE INVENTION

The instant invention relates to reforming and dehydrocyclizationcatalysts and processes employing such catalysts. The term "medium pore"or the prefix "MP-" as employed in the instant invention refers tomembers of the class of non-zeolitic molecular sieves ("NZMS") which arecharacterized in their calcined form by an adsorption of isobutane of atleast 2 percent by weight, preferably at least 4 percent by weight, at apartial pressure of 500 torr and a temperature of 20° C. and are alsocharacterized in their calcined form by an adsorption of triethylamineless than about 5 percent by weight at a partial pressure of 2.6 torrand a temperature of 22° C., preferably less than 3 percent by weight.These "medium pore non-zeolitic molecular sieves" are referred to hereinas "MP-NZMS" to reference the class or individually by the prefix "MP-"followed by the particular class member. For example "MP-SAPO" refers toa medium pore silicoaluminophosphate.

NON-ZEOLITIC MOLECULAR SIEVES ("NZMS")

The term "non-zeolitic molecular sieves" or "NZMS" is defined in theinstant invention to include molecular sieves containing frameworktetrahedral units (TO₂) of aluminum (AlO₂), phosphorus (PO₂) and atleast one additional element (EL) as a framework tetrahedral unit(ELO₂). "NZMS" includes the silicoaluminophosphate molecular sieves ofU.S. Pat. No. 4,440,871, "ELAPSO" molecular sieves as disclosed in U.S.Pat. No. 4,793,984 and certain "MeAPO", "FAPO", "TAPO" and "ELAPO"molecular sieves, as hereinafter described. Crystalline metalaluminophosphates (MeAPOs where "Me" is at least one of Mg, Mn, Co andZn) are disclosed in U.S. Pat. No. 4,567,029, crystallineferroaluminophosphates (FAPOs) are disclosed in U.S. Pat. No. 4,554,143,titanium aluminophosphates (TAPOs) are disclosed in U.S. Pat. No.4,500,651, metal aluminophosphates wherein the metal is As, Be, B, Cr,Ga, Ge, Li or V are disclosed in U.S. Pat. No. 4,686,093, and binarymetal aluminophosphates are described in Canadian Patent 1,241,943.ELAPSO molecular sieves also are disclosed in patents drawn to speciesthereof, including but not limited to:

    ______________________________________                                        NZMS          U.S. Pat. No.                                                   ______________________________________                                        AsAPSO        4,894,213                                                       BeAPSO        4,737,353                                                       CoAPSO        4,744,970                                                       CrAPSO        4,738,837                                                       FeAPSO        4,683,217                                                       GaAPSO        4,735,806                                                       MgAPSO        4,882,038                                                       MnAPSO        4,793,833                                                       ZnAPSO        4,935,216                                                       TiAPSO        4,801,309                                                       TiAPSO        4,880,520                                                       ______________________________________                                    

as well as the metal alumino-phospho-silicate molecular sieves of U.S.Pat. No. 4,793,984 and the binary metal alumino-phospho-silicate sievesof U.S. Pat. No. 4,741,892.

The aforementioned patents are incorporated herein by reference thereto.The nomenclature employed herein to refer to the members of theaforementioned NZMSs is consistent with that employed in theaforementioned applications or patents. A particular member of a classis generally referred to as a "-n" species wherein "n" is an integer,e.g., SAPO-11, MeAPO-11 and ELAPSO-31. In the following discussion onNZMSs set forth hereinafter the mole fraction of the NZMS are defined ascompositional values which are plotted in phase diagrams in each of theidentified patents, published applications or copending applications.

The preferred NZMSs are the silicoaluminophosphate molecular sievesdescribed in U.S. Pat. No. 4,440,871. The silicoaluminophosphatemolecular sieves are disclosed as microporous crystallinesilicoaluminophosphates, having a three-dimensional microporousframework structure of PC₂ ⁺, AlO₂, and SiO₂ tetrahedral units, andwhose essential empirical chemical composition on an anhydrous basis is:

    mR:(Si.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Si_(x) Al_(y) P_(z))O₂ and has a value of from 0.02to 0.3; "x", "y" and "z" represent, respectively, the mole fractions ofsilicon, aluminum and phosphorus present in the oxide moiety, said molefractions being within the compositional area bounded by points A, B, C,D and E on the ternary diagram which is FIG. 1 of U.S. Pat. No.4,440,871, and represent the following values for "x", "y" and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.47   0.52                                            B        0.94          0.01   0.05                                            C        0.98          0.01   0.01                                            D        0.39          0.60   0.01                                            E        0.01          0.60   0.39                                            ______________________________________                                    

The silicoaluminophosphates of U.S. Pat. No. 4,440,871 are generallyreferred to therein as "SAPO" as a class, or as "SAPO-n" wherein "n" isan integer denoting a particular SAPO such as SAPO-11, SAPO-31, SAPO-40and SAPO-41. The especially preferred species SAPO-11 as referred toherein is a silicoaluminophosphate having a characteristic X-ray powderdiffraction pattern which contains at least the d-spacings set forthbelow:

    ______________________________________                                        SAPO-11                                                                                                 Relative                                            2r               d        lntensity                                           ______________________________________                                         9.4-9.65        9.41-9.17                                                                              m                                                   20.3-20.6        4.37-4.31                                                                              m                                                   21.0-21.3        4.23-4.17                                                                              vs                                                  21.1-22.35       4.02-3.99                                                                              m                                                   22.5-22.9 (doublet)                                                                            3.95-3.92                                                                              m                                                   23.15-23.35      3.84-3.81                                                                              m-s                                                 ______________________________________                                    

Ferroaluminophosphates are disclosed in U.S. Pat. No. 4,554,143,incorporated herein by reference, and have a three-dimensionalmicroporous crystal framework structure of AlO₂, FeO₂, and PO₂tetrahedral units and have an essential empirical chemical composition,on an anhydrous basis, of:

    mR:(Fe.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (Fe_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular ferroaluminophosphate involved; "x", "y",and "z" represent the mole fractions of iron, aluminum and phosphorus,respectively, present as tetrahedral oxides, representing the followingvalues for "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.39   0.60                                            C        0.35          0.05   0.60                                            D        0.35          0.60   0.05                                            ______________________________________                                    

When synthesized the minimum value of "m" in the formula above is 0.02.The iron of the FeO₂ structural units can be in either the ferric orferrous valence state, depending largely upon the source of the iron inthe synthesis gel. Thus, an FeO₂ tetrahedron in the structure can have anet charge of either -1 or -2. While it is believed that the Fe, Al andP framework constituents are present in tetrahedral coordination withoxygen (and are referred to herein as such), it is theoreticallypossible that some minor fraction of these framework constituents arepresent in coordination with five or six oxygen atoms. It is not,moreover, necessarily the case that all of the Fe, Al and/or P contentof any given synthesized product is a part of the framework in theaforesaid types of coordination with oxygen. Some of each constituentmay be merely occluded or in some as yet undetermined form, and may ormay not be structurally significant.

For convenience in describing the ferroaluminophosphates, the"short-hand" acronym "FAPO" is sometimes employed hereinafter. Toidentify the various structural species which make up the generic classFAPO, each species is assigned a number and is identified, for example,as FAPO-11, FAPO-31 and so forth.

MeAPO molecular sieves are crystalline microporous aluminophosphates inwhich the substituent metal is one of a mixture of two or more divalentmetals of the group magnesium, manganese, zinc and cobalt and aredisclosed in U.S. Pat. No. 4,567,029. Members of this novel class ofcompositions have a three-dimensional microporous crystal frameworkstructure of MO⁻².sbsp.2, AlO⁻.sbsp.2 and PO₂ ⁺ tetrahedral units andhave an essential empirical chemical composition, on an anhydrous basis,of:

    mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the moles of "R"present per mole of (M_(x) Al_(y) P_(z))O₂ and has a value of from zeroto 0.3, the maximum value in each case depending upon the moleculardimensions of the templating agent and the available void volume of thepore system of the particular metal aluminophosphate involved; "x", "y",and "z" represent the mole fractions of the metal "M", (i.e., magnesium,manganese, zinc and cobalt), aluminum and phosphorus, respectively,present as tetrahedral oxides, said mole fractions being such that theyare within the following limiting values for "x", "y", and "z":

    ______________________________________                                               Mole Fraction                                                          Point    x             y      z                                               ______________________________________                                        A        0.01          0.60   0.39                                            B        0.01          0.39   0.60                                            C        0.35          0.05   0.60                                            D        0.35          0.60   0.05                                            ______________________________________                                    

When synthesized the minimum value of "m" in the formula above is 0.02.

The CoAPSO molecular sieves of U.S. Pat. No. 4,744,970 havethree-dimensional microporous framework structures of CoO₂ ⁻², AlO₂ ⁻,PO₂ ⁺ and SiO₂ tetrahedral units and have an empirical chemicalcomposition on an anhydrous basis expressed by the formula:

    mR:(Co.sub.w Al.sub.x P.sub.y Si.sub.z)O.sub.2

wherein "R" represents at least one organic templating agent present inthe intracrystalline pore system; "m" represents the molar amount of "R"present per mole of (Co_(w) Al_(x) P_(y) Si_(z))O₂ and has a value offrom zero to about 0.3; and "w", "x", "y" and "z" represent the molefractions of cobalt, aluminum, phosphorus and silicon, respectively,present as tetrahedral oxides, where the mole fractions "w", "x", "y"and "z" are each at least 0.01 and are generally defined, as beingwithin the limiting compositional values or points as follows:

    ______________________________________                                               Mole Fraction                                                          Point    x            y      (z + w)                                          ______________________________________                                        A        0.60         0.38   0.02                                             B        0.38         0.60   0.02                                             C        0.01         0.60   0.39                                             D        0.01         0.01   0.98                                             E        0.60         0.01   0.39                                             ______________________________________                                    

It is within the scope of the invention that the catalyst comprises twoor more NZMSs. Optionally these NZMSs are as a multi-compositional,multi-phase composite having contiguous phases, a common crystalframework structure and exhibiting a distinct heterogeneity incomposition, especially wherein one phase comprises a depositionsubstrate upon which another phase is deposited as an outer layer. Suchcomposites are described in U.S. Pat. No. 4,861,739, incorporated hereinby reference thereto. In a highly preferred embodiment the layeredcatalyst comprises a crystalline aluminophosphate of U.S. Pat. No.4,310,440 and a SAPO, especially ALPO-11 and SAPO-11.

MP-NZMS MOLECULAR SIEVES

The specific NZMSs employed in the instant invention are members of theclasses described hereinabove and are characterized in their calcinedform by an adsorption of isobutane of at least 2 percent by weight,preferably at least 4 percent by weight, at a partial pressure of 500torr and a temperature of 20° C. and, further, by an adsorption oftriethylamine of less than 5 percent by weight, preferably less than 3percent by weight, at a partial pressure of 2.6 torr and at atemperature of 22° C.

The adsorption characteristics relate to the pore size or dimension, orcrystallographic free diameter as described in the Atlas of ZeoliteStructure Types, 1987 Edition issued by the Structure Commission of theInternational Zeolite Association. Recognizing that the effective freediameter may depend to some extent on such factors as hydration stateand temperature, the maximum pore dimension of medium-pore NZMSsemployed in the instant invention generally will be no more than about 7Å, and more usually about 6.5 Å, or less. For convenient reference, themedium-pore NZMSs which are characterized by the aforementionedadsorption criteria are denominated herein as "MP-NZMS" or as a class as"MP-NZMSs".

As aforementioned, the MP-NZMSs employed herein are characterized by theaforementioned adsorption criteria for isobutane and triethylamine.Specific MP-NZMS species which may be employed herein include MP-NZMSsin one or more of the aforementioned subclasses and having a "-n"designation of -11, -31, -40, and -41. MP-NZMSs include, but are notlimited to, ELAPSO-11, ELAPSO-31, ELAPSO-40, ELAPSO-41, CoAPSO-11,CoAPSO-31, FeAPSO-11, FeAPSO-31, MgAPSO-11, MgAPSO-31, MnAPSO-11,MnAPSO-31, TiAPSO-11, ZnAPSO-11, ZnAPSO-31, CoMgAPSO-11, CoMnMgAPSO-11,MeAPO-11, TiAPO-11, TiAPO-31, ELAPO-11, ELAPO-31, ELAPO-40, ELAPO-41SAPO-11, SAPO-31, SAPO-40 and SAPO-41.

The characterization of the NZMSs employed in the instant inventionrelates to an adsorption characterization that is carried out on a NZMSwhich has been subjected to a post synthesis treatment, e.g.,calcination, to remove a substantial portion of the template "R" whichis present as a result of synthesis. Although a particular MP-NZMS ischaracterized herein by reference to its adsorption of isobutane ortriethylamine as being to the adsorption characteristics of the MP-NZMSin its calcined form, the instant invention necessarily includes the useof a non-calcined or modified MP-NZMSs which are characterized by suchadsorption in a modified or calcined form, since upon use of such anon-calcined MP-NZMS in the instant process at effective reformingconditions the NZMS may be calcined or hydrothermally treated in situ soas to have the characteristic adsorptions of isobutane andtriethylamine. Thus, the NZMS may be rendered in situ to a formcharacterized by the aforementioned adsorption characteristics and,accordingly, such is within the scope of the instant invention. Forexample, an as-synthesized MnAPO-11 or MgAPSO-11 is not characterized bythe aforementioned adsorption characteristics due to the presence oftemplate "R" which is present as a result of synthesis, although thecalcined form of MnAPO-11 and MgAPSO-11 are characterized by theaforementioned adsorption of isobutane and triethylamine. Thus,reference to a MP-NZMS having a particular adsorption characteristic inits calcined form is not intended to exclude the use of the MP-NZMS inits as-synthesized form which upon in situ calcination, hydrothermaltreatment and/or other treatment, e.g., ion exchange with suitableatoms, would have such adsorption characteristics.

MP-NZMS-CONTAINING CATALYSTS

The MP-NZMS may be employed in conjunction with a Group VIII metal as areforming/dehydrocyclization catalyst or may be employed in conjunctionwith a metal/chlorinated-alumina catalyst(s) as generally employedheretofore as reforming catalysts. In one embodiment a MP-NZMS isemployed with a traditional reforming catalyst comprising a Group VIIImetal and a chlorinated carrier, e.g., an alumina. The term "carrier" isemployed herein in its common meaning to denote a support material forthe metal component of the reforming catalyst. In this embodiment theGroup VIII metal is generally present in an effective amount from about0.1 to about 2, preferably from about 0.2 and about 1.2 percent byweight (wt. %), more preferably between about 0.2 and 0.8 wt. %, basedon the weight of the carrier, with from about 0.1-2% by weight halogen,preferably chlorine being present, based on the weight of the carrier,e.g., an alumina. (reference to "chlorine" and/or "chlorinated" hereinis intended to include the other halogens.) The MP-NZMS component may bepresent in an amount between about 1 and about 99.9 percent by weight(wt. %), is preferably present in an amount between about 5 and about 70wt. % and more preferably between about 5 and 40 wt. %, based on thetotal weight of the catalyst. When a halogenated carrier component ispresent such as may be present in an effective amount between about 5and about 95 percent by weight and is preferably present in an effectiveamount of at least 40 percent by weight, based on the total catalystweight.

The MP-NZMS-containing catalysts contain an effective amount of one ormore Group VIII metals, e.g., nickel, ruthenium, rhodium, palladium,iridium or platinum. In one embodiment the MP-NZMS is employed in acatalyst comprising a first Group VIII metal in conjunction with asecond metal component to form a bi-metallic catalyst and, optionally,may also be used with the aforementioned chlorinated-alumina component.The catalyst may contain as the second metal component a second GroupVIII metal, a transition metals such as rhenium, tungsten, and/or ametal such as tin or germanium.

The preferred Group VIII metal for use herein is platinum.Platinum-containing catalysts generally exhibit high selectivity to highoctane products. The percentage of platinum in the catalyst is generallybetween about 0.1 wt. % and about 2 wt. % and preferably between about0.2 and about 1.2 wt. %, and most preferably between about 0.2 to 0.8,based on the total catalyst weight. In the prior art it has beenobserved that the lower limit corresponds to a lower catalyst activityand the upper limit to higher catalyst activity. When a second metalcomponent is employed, the weight ratio of the Group VIII metal, e.g.platinum, to such second metal, including a second Group VIII metal orrhenium, is between about 1:5 and about 5:1 and is preferably betweenabout 1:2 and about 2:1. The total amount of the metal components willbe in the aforementioned ranges.

The metal component(s) of the MP-NZMS-containing catalyst is generallyintroduced by means of impregnation using an aqueous solution of anappropriate salt of the desired metal(s). When it is desired tointroduce two metal components, the operation may be carried outsimultaneously or sequentially. The addition of the metal component(s)to the instant reforming catalyst depends in part on the formulation ofthe reforming catalyst. If it is advantageous that the MP-NZMS beemployed as the carrier for the metal component, the metal component mayfavorably be added to the MP-NZMS before the MP-NZMS is calcined toremove the organic templating agent present as a result of the MP-NZMSsynthesis. It is believed that the addition of the metal to thetemplate-containing MP-NZMS affects the distribution of the metal in afavorable way by preventing the metal species from blocking the pores ofthe MP-NZMS and affecting the activity of the MP-NZMS. It is believedthat when the metal component is added to the MP-NZMS, acting as thecarrier for the metal component, as a cationic species, that it ispreferred to add such cationic metal component prior to calcination ofthe MP-NZMS whereby organic templating agent is removed, such beingpresent as a result of the synthesis of the MP-NZMS. This procedure isbelieved to aid in preventing blockage of the pores of the MP-NZMS bycationic metal species. It is believed that the calcined form of theMP-NZMSs may be employed as the carrier for the metal component whenanionic metal species are employed as the source of the metal component.When the metal component of the catalyst is added by addition to aseparate carrier component, such as an alumina, to form a discretecomponent, the metal/carrier component is admixed with the MP-NZMS. Themixture may then be mixed with a binder, e.g., a silica, if any, andformed, e.g., by coextrusion, into the final catalyst. In anotherembodiment, an as-synthesized MP-NZMS (containing template) and acarrier may be mixed prior to the impregnation or other introduction ofthe metal component. The template can then be removed by calcinationunder conditions effective for the removal of the organic templatingagent from the MP-NZMS.

By way of example, platinum can be introduced to the catalyst byimpregnating (or other suitable addition process) a carrier, e.g., agamma-alumina, or a MP-NZMS, e.g., SAPO-11, with an aqueous solution oftetramineplatinum (II) nitrate, chloroplatinic add, chloroplatinousacid, dinitrodiamino-platinum, tetramineplatinum (II) chloride, anionicplatinum complexes or cationic platinum complexes (such astetramineplatinum (II) nitrate). Similar compounds of the other metalcomponents may be employed. The use of a halogen containing (e.g.,chlorine) salt or complex of platinum is generally beneficial inproviding halogen (e.g., chloride or chloro-species) component, if anyis desired, in the final catalyst.

An inorganic oxide is generally employed as a carrier for the metalcomponent. In addition, an inorganic oxide may be employed, as anoptional component, as a binder component for the final catalyst. Theinorganic oxides employable as a carrier for the metal and/or as amatrix component and/or as a binder component can be a natural orsynthetically produced inorganic oxide or combination of inorganicoxides. Typical inorganic oxides which can be used include clays,aluminas, silicas, silica-aluminas, titanias, magnesia, alumina-boria,alumina-titania, and mixtures thereof. The preferred inorganic oxidecarrier for the metal component(s) is believed to be an alumina, andmore preferably a gamma-alumina. The preferred binder components arebelieved to be aluminas and silicas. The inorganic oxide componentpresent as a binder or matrix component may be present in an amount fromzero (0) to about 25 weight percent, based on the total catalyst weight,said amount not including any inorganic oxide present as a carrier forthe metal component. In one embodiment, a MP-NZMS is preferably added tothe metal/chlorinated carrier component as a separate component.

The MP-NZMS-containing catalysts can be employed in any of theconventional catalyst forms known to the art for reforming and/ordehydrocyclization catalysts, including pills, pellets, granules, brokenfragments, or various special shapes. The catalysts can be employed inheretofore employed bed configurations including a fixed bed within areaction zone, and the charging stock may be passed therethrough in theliquid, vapor (preferably the vapor phase), or mixed phase in eitherupward or downward flow. Alternatively, the catalyst may be prepared ina suitable form for use in moving beds, or in fluidized-solid processes,in which the charging stock is passed upward through a turbulent bed offinely divided catalyst. The instant catalyst(s) may be used insemi-regenerative, cyclic, semicyclic, or continuous reformingprocesses. Such processes are well known. The reaction products from anyof the foregoing processes are charged to a separator for removal oflight gases, and fractionated to recover the various components thereof.

In one embodiment the MP-NZMS-containing catalyst(s) of the instantinvention may be employed in a tail reactor as the last catalyst bed ina process employing multiple catalyst beds. The first catalyst in suchan embodiment would comprise a traditional reforming and/ordehydrocyclization catalyst and would generally be the same catalyst asemployed in the instant process, except such would not contain theMP-SAPO component.

After the desired metal(s) has been introduced, the catalyst istypically treated in air at about 400° to 600° C., preferably about 500°C.±50° C., and then reduced in the presence of a hydrogen-containing gasat temperatures of between about 200° C. and about 700° C., preferablybetween about 350° C. and about 500° C.

In some instances the selectivity of a MP-NZMS-containing catalyst maybenefit from an initial deactivation by steaming, coking or by treatmentwith sulfur compounds. Such deactivation methods are well known in theart to provide improved selectivity by decreasing the initial activityof the catalyst.

FEEDSTOCKS

The feedstock in reforming is typically a mixed hydrocarbon fractioncontaining significant quantities of paraffinic hydrocarbons, commonlyavailable in a typical refinery. Suitable feedstocks include, naphthas(virgin, cracked or Fischer-Tropsch), highly paraffinic straight-runnaphthas, paraffinic raffinates from aromatic extraction or adsorption,upstream reformate feedstocks, heavy hydrocracked gasoline fractions, C₆-C₉ paraffin-rich streams and the like refinery streams. In the case ofcracked naphthas, the naphtha is generally hydrogenated prior to use toreduce the presence of olefinic compounds. In a typical reformingoperation the feedstock is a naphtha or petroleum fraction boiling inthe range of between about 80° F. and about 450° F., and preferablybetween about 180° F. and about 380° F. Such fractions usually containfrom about 20 to about 80 volume % paraffins, both normal and branched,which fall in the range of about C₅ to C₁₂. In one embodiment, thefeedstock contains paraffinic hydrocarbons having about 6 to 12 carbonatoms per molecule. It is to be understood that such acyclichydrocarbons can be charged individually, in admixture with one or moreof the other acyclic hydrocarbons, or in admixture or as components ofother hydrocarbon mixtures such as naphthenes, aromatics and the like.

Feedstocks comprising essentially acyclic hydrocarbons may be employedherein if dehydrocyclization is the desired reaction and can in generalbe any acyclic hydrocarbon capable of undergoing ring-closure to producean aromatic hydrocarbon. That is, it is intended to include within thescope of the present invention, the dehydrocyclization of any acyclichydrocarbon capable of undergoing ring-closure to produce an aromatichydrocarbon under effective process conditions for reforming and/ordehydrocyclization. More particularly, suitable acyclic hydrocarbonsinclude acyclic hydrocarbons containing 6 or more carbon atoms permolecule such as C₆ -C₁₂ paraffins. Specific examples of suitableacyclic hydrocarbons are paraffins such as n-hexane, 2-methylpentane,3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane,3-ethylpentane, 2,5-dimethylhexane, n-octane, 2-methylheptane,3-methylheptane, 4-methylheptane, 3-ethylhexane, n-nonane,2-methyloctane, 3-methyloctane, n-decane and the like compounds.

Preferably, the feedstocks employed in reforming are substantially freeof sulfur, nitrogen, metals, and other known poisons for reformingcatalysts. The feedstock can have sulfur, nitrogen, metals, and otherknown poisons removed by conventional hydrotreating techniques plussorbers that remove such compounds.

In the case of a feedstock which is not already low in sulfur,acceptable sulfur levels can be obtained by hydrofining the feedstock ina pretreatment zone where the naphtha is contacted with a hydrofiningcatalyst which is resistant to sulfur poisoning. A suitable catalyst forhydrodesulfurization is, for example, an alumina-containing supportcontaining molybdenum oxide, cobalt oxide and/or nickel oxide.Hydrodesulfurization is ordinarily conducted at 315° C. to 455° C., at200 to 2000 psig, and at a liquid hourly space velocity of 1 to 5. Thesulfur and nitrogen contained in the naphtha are converted to hydrogensulfide and ammonia, respectively, which can be removed prior toreforming by suitable conventional processes.

REFORMING PROCESSES

Reforming processes may be carried out over a wide range of effectivereforming process conditions. The actual process conditions depend onthe particular reforming catalyst, the feedstock, the desired products,the reforming process design and the like. Process conditions forCatalytic reforming, Magnaforming, Platforming, Powerforming,Rheniforming and Ultraforming are well known in the art (see:"Hydrocarbon Processing," September 1982, at pages 164, 165, 166, 167,168 and 169, respectively; incorporated herein by reference).Magnaforming is described at pages 111 to 114 of "HydrocarbonProcessing," June 1974 (incorporated herein by reference). A descriptionof a representative reforming process is disclosed in U.S. Pat. No.4,018,711 at column 5, line 19 to column 6, line 50, said passageincorporated herein by reference. The pertinent section of thisreference cites reforming operating conditions as an inlet temperatureof about 700° F. to about 1000° F., preferably, within the range of 850°F. to about 1050° F.; a pressure ranging from atmospheric to about 1000psig, preferably from about 50 psig to 500 psig; a WHSV of at least 0.5weight unit of hydrocarbon per hour per weight unit of catalyst,preferably of at least 1 weight unit of hydrocarbon per hour per weightunit of catalyst; and a recycle gas rate within the range of about 1,000SCFB to about 20,000 SCFB, preferably from about 3,000 SCFB to about10,000 SCF/B.

The feedstock is contacted with the molecular-sieve reforming catalystof the invention under effective reforming conditions as heretoforeemployed in the prior art. This contacting may be accomplished by usingthe catalyst in a fixed bed system, a moving bed system, a fluidizedsystem, or in a batch-type operation. In a fixed bed system, thefeedstock is preheated by any suitable heating means to the effectivereforming process temperature and pressure and then passed into areforming zone containing a bed of the catalyst. It is, of course,understood that the reforming process may be one or more separatereactors with suitable means therebetween to ensure that the desiredconversion temperature is maintained at the entrance to each reactor. Itis also important to note that the reforming feedstock may be contactedwith the catalyst bed in either upward, downward, or radial flowfashion. In addition, the reactants may be in a liquid phase, a mixedliquid-vapor phase, or a vapor phase when they contact the catalyst. Areforming process typically comprises two or more fixed beds ordense-phase moving beds of the catalyst. In a multiple bed system, itis, of course, within the scope of the present invention to use thepresent catalyst in less than all of the beds with a primary, usuallybifunctional, reforming catalyst being used in one or more upstream bedsof the multi-bed system. The reforming zone may be one or more separatereactors with suitable heating means therebetween to compensate for theendothermic nature of the reforming process that takes place in eachcatalyst bed.

In the embodiment in which a primary reforming catalyst is used in oneor more upstream beds, the mixed hydrocarbon fraction first contacts theprimary reforming catalyst at primary reforming conditions to obtain anaromatics-rich intermediate. The primary reforming catalyst comprises aneffective amount of a platinum-group metal component supported on arefractory inorganic oxide. The platinum-group metal preferably isplatinum, and is present in the first reforming catalyst on an elementalbasis of between about 0.1 and 2 wt. %, based on the total weight of thecatalyst. The primary reforming catalyst also may contain effectiveamounts of other metal components comprising rhenium, indium, Group IVAmetals such as germanium, tin and lead, and alkali or alkaline earthmetals; effective amounts are between about 0.1 and 5 wt. % of thecatalyst as total metals on an elemental basis. A halogen component,especially chlorine, may be present in an amount of about 0.2 to 15 wt.% of the catalyst on an elemental basis. Primary reforming conditionscomprise a temperature of about 700° to 1040° F., a pressure of fromabout atmospheric to 1000 psig, a WHSV of from about 0.2 to 10 weightunit of hydrocarbon per hour per weight unit of catalyst, and a recyclegas rate within the range of about 100 to 20,000 SCFB. Further detailsof primary reforming catalysts and processes may be found in U.S. Pat.Nos. 4,677,094 and 4,929,333, incorporated herein by reference, thelatter of which also contains teachings relevant to the use of differentreforming catalysts in multiple catalyst zones.

The aromatics-rich intermediate from primary reforming contacts themolecular-sieve reforming catalyst as described hereinabove to obtain ahigher-octane product. Optimally the primary reforming catalyst and themolecular-sieve reforming catalyst are contained in the same hydrogencircuit, i.e., hydrogen is not separated between these two reformingsteps. The molecular-sieve reforming catalyst containing a MP-NZMSpreferably is contained in a downstream reactor, most preferably aterminal, or last reactor of a multi-reactor reforming process. It isespecially preferred that a primary reforming catalyst having an absenceof a MP-NZMS is contained in upstream reactors.

Reforming generally results in the production of hydrogen. Thus,exogenous hydrogen need not necessarily be added to the reforming systemexcept for pre-reduction of the catalyst and when the feed is firstintroduced. Generally, once reforming is underway, part of the hydrogenproduced is recirculated over the catalyst. The presence of hydrogen isgenerally understood in the art to reduce the formation of coke whichtends to deactivate the catalyst. Hydrogen is preferably introduced intothe reforming reactor(s) at a rate varying from greater than zero toabout 30 moles of hydrogen per mole of feedstock. The hydrogen can beadded in admixture with light gaseous hydrocarbons.

Although hydrogen may be used, in some cases other art-recognizeddiluents may be advantageously utilized, either individually or inadmixture with hydrogen. Other diluents include C₁ to C₅ paraffins suchas methane, ethane, propane, butane and pentane and mixtures thereof.If, after a period of operation, the reforming catalyst has becomedeactivated by the presence of carbonaceous deposits, said deposits canbe removed from the catalyst by passing an oxygen-containing gas, suchas dilute air. Chlorine and/or chloro-compounds (in the presence of anoxygen-containing gas) are generally brought into contact with thecatalyst to aid in redistribution of metal components present in thecatalyst, if necessary. Regeneration of the MP-NZMS-containing catalystmay be performed in the semi-regenerative mode in which the reformingoperation is interrupted after a period of time and catalystregeneration is carried out, or in the onstream regenerative mode, inwhich a portion of the catalyst is regenerated while the reformingoperation is continued over the remainder of the catalyst. Two types ofonstream regeneration are generally known in the prior art, cyclic andcontinuous (in situ regeneration). In cyclic reforming, the catalyst inone of a series of reactors is regenerated while reforming is continuedin the remainder of the reactors. In continuous reforming, a portion ofdeactivated catalyst is removed from operation, regenerated in aseparate regeneration system while reforming is continued, and theregenerated catalyst is then returned to the reforming operation. Themethod of regenerating the catalyst will depend on whether there is afixed bed, moving bed, or fluidized bed operation and the particularprocess constraints of the refiner. Regeneration methods and conditionsfor reforming are well known in the art and such are generallyemployable with the instant MP-NZMS-containing catalysts.

In the following examples the products were evaluated in severalrespects by determining: ##EQU1## where "i" is a component and "n" isthe number of components present in the products. ##EQU2##

The Research Octane Number (RON) of the C₅ + product (productscontaining five or more carbons) was calculated using the publishedoctane numbers for individual C₅ +components and from their volumepercent in the C₅ +product. The volume % of individual C₅ +componentswas calculated as follows: ##EQU3## where "g" is a particular componentin products and "i" represents all components summed over all "n"components in C₅ + products.

The calculated RON was determined for the C₅ + product according to:##EQU4## where "RON_(i) " is the blending research octane numbers forcomponent "i".

The following examples are provided to illustrate the invention and arenot intended to be limiting thereof:

EXAMPLE 1

a) A reference catalyst (denominated "Reference Catalyst A") wasprepared with a CATAPAL (pseudoboehmite) alumina (CATAPAL is a trademarkof Condea Alumina SB). which was calcined in air at 200° C. for 4 hoursand heated for 16 hours at 540° C. to form a gamma-alumina. A twentyfour-gram sample of the gamma alumina was impregnated with a solutioncontaining 0.48 grams of H₂ PtCl₂ and 0.96 grams of Al(NO₃)₃ in 8.4grams of water. The alumina and the H₂ PtCl₂ solution were mulled, driedat room temperature for one hour, remulled and then dried at 121° C. for16 hours. The dried product (Pt/Cl-alumina component) was then calcinedin air at 260° C. for two hours. The calcined product was formed into1/16" extrudates by mixture with SiO₂ and the final extrudates contained20 wt. % SiO₂ (LUDOX AS 40) binder. The SiO₂ was gelled prior to usewith ammonium acetate (1 ml. of 16.7 wt. % ammonium acetate per gram ofSiO₂. The extrudates were dried in air at 110° C. overnight for 16 hoursand calcined in air at 540° C. for 3 hours. The extrudates were groundto form a 40-60mesh (U.S. Standard). Reference Catalyst A contained thefollowing amounts of platinum and chloride:

    ______________________________________                                        Wt. %                                                                         ______________________________________                                                 Pt  0.63                                                                      Cl  0.25                                                             ______________________________________                                    

b) A catalyst according to the instant invention was prepared bypreparing a mixture containing 60 wt. % of the Pt/Cl-alumina component,as prepared in part (a) in the preparation of Reference Catalyst A, and40 wt. % of a SAPO-11, as disclosed in U.S. Pat. No. 4,440,871.

SAPO-11 was prepared according to example 17 of U.S. Pat. No. 4,440,871,except that the crystallization time was 24 hours instead of 48 hours. Areaction mixture was prepared by combining 23.06 grams of 85 wt. %orthophosphoric acid (H₃ PO₄) and 23.06 grams of water, to which wasadded 13.81 grams of a hydrated aluminum oxide (a pseudoboehmite phase,74.2 wt. % Al₂ O₃, 25.8 wt. % H₂ O) and stirred until homogeneous. Tothis mixture was added a mixture of 3.90 grams of a fumed silica (92.8wt. % SiO₂, 7.2 wt. % H₂ O) in 103.5 grams of a solution of 25.0 wt. %tetra-n-butylammonium hydroxide (TBAOH) in methanol. This mixture wasstirred until homogeneous and then 20.41 grams of di-n-propylamine wasadded with stirring until a homogeneous mixture was obtained. Thecomposition of the final reaction mixture in molar oxide ratios was:

    2.0Pr.sub.2 NH: 0.5(TBA).sub.2 O: Al.sub.2 O.sub.3 : P.sub.2 O.sub.5 : 0.6SiO.sub.2 : 16.75H.sub.2 O: 24.3CH.sub.3 OH

A portion of the reaction mixture was placed in a stainless steelpressure vessel lined with an inert plastic material and heated in anoven at 200° C. at autogenous pressure for 24 hours. The solid reactionproduct was recovered by centrifuging, washing with water, and was thendried in air at room temperature. A portion of the solids was submittedfor X-ray and chemical analysis and gave an X-ray powder diffractionpattern representative of SAPO-11. By chemical analysis, the compositionwas found to be 31.5 wt. % Al₂ O₃, 40.9 wt. % P₂ O₅, 12.0 wt. % SiO₂,8.1 wt. % C, 1.2 wt. % N, and 13.9 wt. % LOI. The SAPO-11 product wasthen calcined at above 450° C. in air to remove the organic templatingagent.

The SAPO-11 and Pt/Cl-alumina component were mixed with 20 wt. % SiO₂binder, as discussed in part (a), and extruded. The extrudate was driedat 110° C. overnight (N16 hours) and calcined in air at 540° C. for 3hours. This catalyst was denominated "Catalyst B".

c) A Comparative Catalyst (containing SAPO-5) was prepared according tothe procedure employed in part (b), except SAPO-5 was employed in placeof SAPO-11. SAPO-5 was prepared according to examples 9 and 11 of U.S.Pat. No. 4,440,871, except that the organic templating agent wastetrapropylammonium hydroxide, the gel SiO₂ /Al₂ O₃ ratio was 0.6 andthe gel contained 40 H₂ O. The reaction mixture was prepared bycombining triethylphosphate and water, to which was added apseudoboehmite alumina. The mixture was stirred until homogeneous. Tothis mixture was added a dispersion of a fumed silica (92.8 wt. % SiO₂,7.2 wt. % H₂ O), and an aqueous solution of 40% tetra-n-propylammoniumhydroxide (TPAOH), and the mixture stirred until homogeneous. Thecomposition of the final reaction mixture in molar oxide ratios was:

    Al.sub.2 O.sub.3 :P.sub.2 O.sub.5 :0.6SiO.sub.2 :(TPA).sub.2 O: 40H.sub.2 O

A portion of the reaction mixture was sealed in a stainless steelpressure vessel lined with an inert plastic material and heated in anoven at 200° C. at autogenous pressure for 24 hours. The solid reactionproduct was recovered by centrifuging, washing with water and then driedin air at room temperature. The product was analyzed and gave an X-raypowder diffraction pattern characteristic of SAPO-5. The product wascalcined at above 450° C. in air to remove organic templating agent.This catalyst was denominated "Catalyst C".

EXAMPLE 2

The catalysts prepared in example 1 were evaluated as dehydrocyclizationcatalysts using a technical grade n-hexane feedstock containing, in wt.%:

    ______________________________________                                        n-hexane              86.357                                                  methylcyclopentane    9.694                                                   3-methylpentane       3.741                                                   2-methylpentane       0.207                                                   RON (Research Octane Number)                                                                        29.27                                                   ______________________________________                                    

The catalysts (A, B and C) were evaluated using a micro reactorcomprising a stainless steel tube (1/8" (ID)) and using about 0.350 to0.359 grams of the selected catalyst (40×60 mesh, U.S. Standard). Theselected catalyst was heated to 900° F. over 21/2 to 3 hours under H2(120 ml/min 100 psig) and held at 900° F. for one hour and cooled to860° F. The H2 was lowered to 75 ml./min. and the feed was thenintroduced into the micro reactor. The micro reactor was maintained atthe process temperature by a fluidized sandbath.

Each catalyst was evaluated by preheating the micro reactor at atemperature of about 860° F. or at about 900° F. The n-hexane feed wasthen introduced at a pressure of 100 psig, a Weight Hourly SpaceVelocity (WHSV) of 7.7 and a hydrogen/feed molar ratio of 5.4. Productswere collected at selected run times and the products were analyzed bygas chromatography. The weight percent products and other reportedvalues were computed on the basis of a 100% material balance. The volume% was calculated using product densities and assuming no volume changesoccurred upon mixing of product components. The RON of the feedstock andproducts was calculated using the calculated volume percents and theblending research octane numbers of the individual components.

The results of the evaluation of Catalysts A, B and C are set forth inTables I, II and III for each catalyst, respectively, at temperatures of860° F. (Tables I-1, II-1 and III-1) and 900° F. Tables I-2, II-2 andIII-2). The results, as set forth in Tables I, II and III, demonstratethe dramatic effect that SAPO-11 has in a reforming/dehydrocydizationprocess when employed with a Pt/Cl-alumina-type catalyst. The SAPO-11provides an improvement in the ratio of benzene to lights ("lights" areC₁ to C₅ products) and iso-C₆ s to lights as a function of theconversion. FIGS. 1 and 2 graphically depict the ratios of iso-C₆s/lights and benzene/lights as a function of n-hexane conversion forCatalysts A, B and C.

FIG. 3 and FIG. 4 (containing different scales) graphically depict thevolume % yield as a function of the Research Octane Number (RON) forCatalysts A, B and C. The RON (calculated) and C₅ +Yield for eachcatalyst was calculated using the components containing five or morecarbon atoms, as above described.

For Reference Catalyst A, the average of the two data points at 20 and21 hours from Table I-1 showed that 95.05 weight percent of the totalhydrocarbon product is C₅ or C₆ and the C₅ + product is 95.23 volumepercent of the n-hexane feed from which it was derived. The calculatedRON for the C₅ + product was 40.41. Table I-2 shows that thecorresponding values for a 900° F. reaction temperature were 94.22weight percent C₅ +, 93.89 volume percent C₅ + and a RON of 45.00.Analysis of the sample taken at 20 hours in Table I-1 gave a 94.9 weightpercent C₅ -C₆ product (95.1 volume percent), a calculated RON of 39.7,1.7 weight percent benzene, 20.7 weight percent isohexanes (ISO), 5.2weight percent C₁ -C₄ gases (HC), and ISO/HC ratio of 4.1 and abenzene/HC ratio of 0.37.

The results for Catalyst B (SAPO-11) in Table II-1 at 20 hours gave a97.4 weight percent yield (96.9 volume percent), a calculated RON of55.4, 2.9 weight percent benzene, 39.4 weight percent isohexanes (ISO),2.6 weight percent C₁ -C₄ gases (HC), an ISO/HC weight ratio of 15.0 anda benzene/HC ratio of 1.1. These results demonstrate the improvedselectivity to higher octane products of Catalyst B, as compared toCatalyst A. The improvement in the calculated RON of the products from39.7 to 55.4 occurred with a concurrent increase in the yield (weightpercent and volume percent).

The results for Comparative Catalyst C (containing SAPO-5) for theproduct sampled at 20.25 hours in Table III-1 gave a 97.1 weight percentyield of C₅ -C₆ products (96.7 volume percent yield), a calculated RONof products of 36.5, 1.0 weight percent benzene, 11.1 weight percentisohexanes (ISO), 2.9 weight percent C₁ -C₄ gases (HC), an ISO/HC ratioof 3.8 and a benzene/HC ratio of 0.35. A comparison of results obtainedby use of Catalyst C and the results obtained by use of ReferenceCatalyst A demonstrates that the addition of SAPO-5 to ReferenceCatalyst A did not improve the selectivity to gasoline products. Incontrast, a comparison of the results from Reference Catalyst A andComparative Catalyst C (SAPO-5) with the results obtained by use ofCatalyst B (SAPO-11) demonstrates the significant improvement that useof Catalyst B (SAPO-11) had on the calculated RON of the products. Thisimprovement is graphically depicted in FIG. 3 where the solid linedenotes Reference Catalyst A and wherein it is shown that Catalyst B(SAPO-11) provides improvement over Reference Catalyst A.

                  TABLE I-1                                                       ______________________________________                                        (Catalyst A(Ref)).sup.1                                                       GC PRODUCT ANALYSIS: (WEIGHT PERCENT):                                        ______________________________________                                        METHANE                 0.83    0.75                                          ETHANE                  0.90    0.79                                          PROPANE                 2.26    2.02                                          ISOBUTANE               0.00    0.05                                          N-BUTANE                1.23    1.07                                          ISO-PENTANE             0.21    0.19                                          N-PENTANE               1.89    1.84                                          TOTAL LIGHTS (C.sub.5.spsb.-)                                                                         7.31    6.72                                          2,2 DIMETHYL BUTANE     0.14    0.15                                          2 METHYL PENTANE        11.23   11.66                                         3 METHYL PENTANE        9.32    9.83                                          N-HEXANE                65.45   63.78                                         METHYL CYCLOPENTANE (MCP)                                                                             4.88    5.59                                          CYCLOHEXANE             0.00    0.06                                          TOTAL C.sub.6 SATURATES 91.01   91.07                                         BENZENE                 1.67    2.21                                          CALCULATIONS:                                                                 RON (CALCULATED)        40.41.sup.2                                                                           --.sup.2                                      VOLUME % YIELD          95.23.sup.2                                                                           --.sup.2                                      METHANE/PROPANE         0.37    0.37                                          ISO-BUTANE/N-BUTANE     0.00    0.05                                          ISO-PENTANE/N-PENTANE   0.11    0.10                                          CONVERSION (Vol. %)     24.21   26.14                                         BENZENE SEL. %.sup.3    6.91    8.46                                          LIGHTS SEL. %.sup.3     30.20   25.70                                         MCP SEL. %              -19.90  -15.70                                        ISO-C.sub.6 SEL. %.sup.3                                                                              69.15   67.91                                         HOURS ON STREAM         20.0    21.0                                          TEMPERATURE (°F.)                                                                              860     860                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.359 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE I-2                                                       ______________________________________                                        (Catalyst A (Ref.)).sup.1                                                     ______________________________________                                        GC PRODUCT ANALYSIS: (WEIGHT PERCENT):                                        METHANE                0.74    0.92                                           ETHANE                 0.83    1.07                                           PROPANE                1.98    2.48                                           ISOBUTANE              0.07    0.12                                           N-BUTANE               0.96    1.27                                           ISO-PENTANE            0.24    0.24                                           N-PENTANE              1.39    1.58                                           TOTAL LIGHTS (C.sub.5 -)                                                                             6.23    7.68                                           2,2 DIMETHYL BUTANE    0.36    0.35                                           2 METHYL PENTANE       12.90   12.35                                          3 METHYL PENTANE       10.73   10.24                                          N-HEXANE               60.00   59.43                                          METHYL CYCLOPENTANE (MCP)                                                                            6.71    6.61                                           CYCLOHEXANE            0.00    0.00                                           TOTAL C.sub.6 SATURATES                                                                              90.70   88.97                                          BENZENE                3.07    3.35                                           CALCULATIONS:                                                                 RON (CALCULATED)       45.00.sup.2                                                                           --.sup.2                                       VOLUME % YIELD         93.89.sup.2                                                                           --.sup.2                                       METHANE/PROPANE        0.38    0.37                                           ISO-BUTANE/N-BUTANE    0.08    0.10                                           ISO-PENTANE/N-PENTANE  0.17    0.15                                           CONVERSION (Vol. %)    30.52   31.19                                          BENZENE SEL. %.sup.3   10.05   10.74                                          LIGHTS SEL. %.sup.3    20.43   24.62                                          MCP SEL. %             -9.76   -9.90                                          ISO-C.sub.6 SEL. %.sup.3                                                                             65.65   60.90                                          HOURS ON STREAM        25.00   26.25                                          TEMPERATURE (°F.)                                                                             902     901                                            ______________________________________                                         .sup.1 Catalyst Weight: 0.359 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE II-1                                                      ______________________________________                                        (Catalyst B (SAPO-11)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS: (WEIGHT PERCENT):                                        METHANE                0.14    0.21                                           ETHANE                 0.25    0.39                                           PROPANE                1.83    2.93                                           ISOBUTANE              0.06    0.07                                           N-BUTANE               0.35    0.35                                           ISO-PENTANE            0.14    0.11                                           N-PENTANE              0.30    0.27                                           TOTAL LIGHTS (C.sub.5 -)                                                                             3.07    4.33                                           2,2 DIMETHYL BUTANE    0.42    0.31                                           2 METHYL PENTANE       22.31   21.20                                          3 METHYL PENTANE       16.72   16.09                                          N-HEXANE               45.57   46.46                                          METHYL CYCLOPENTANE (MCP)                                                                            8.95    9.02                                           CYCLOHEXANE            0.09    0.07                                           TOTAL C.sub.6 SATURATES                                                                              94.06   93.16                                          BENZENE                2.87    2.51                                           CALCULATIONS:                                                                 RON (CALCULATED)       54.89.sup.2                                                                           --.sup.2                                       VOLUME % YIELD         96.25.sup.2                                                                           --.sup.2                                       METHANE/PROPANE        0.08    0.07                                           ISO-BUTANE/N-BUTANE    0.17    0.20                                           ISO-PENTANE/N-PENTANE  0.47    0.42                                           CONVERSION (Vol %)     47.23   46.19                                          BENZENE SEL. %.sup.3   6.08    5.43                                           LIGHTS SEL. %.sup.3    6.50    9.38                                           MCP SEL. %             -1.57   -1.45                                          ISO-C.sub.6 SEL. %.sup.3                                                                             75.35   73.00                                          HOURS ON STREAM        20.00   23.00                                          TEMPERATURE (°F.)                                                                             862     863.6                                          ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE II-2                                                      ______________________________________                                        (Catalyst B (SAPO-11)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE              0.33    0.24                                             ETHANE               0.69    0.43                                             PROPANE              5.47    2.80                                             ISOBUTANE            0.28    0.11                                             N-BUTANE             0.82    0.58                                             ISO-PENTANE          0.26    0.26                                             N-PENTANE            0.44    0.47                                             TOTAL LIGHTS (C.sub.5 -)                                                                           8.30    4.88                                             2,2 DIMETHYL BUTANE  0.74    0.81                                             2 METHYL PENTANE     22.89   23.59                                            3 METHYL PENTANE     17.58   17.93                                            N-HEXANE             39.11   41.28                                            METHYL CYCLOPENTANE  7.61    7.61                                             CYCLOHEXANE          0.10    0.07                                             TOTAL C.sub.6 SATURATES                                                                            88.02   91.28                                            BENZENE              3.68    3.84                                             CALCULATIONS:                                                                 RON (CALCULATED)     58.00.sup.2                                                                           --.sup.2                                         VOLUME % YIELD       92.50   --.sup.2                                         METHANE/PROPANE      0.06    0.08                                             ISO-BUTANE/N-BUTANE  0.34    0.20                                             ISO-PENTANE/N-PENTANE                                                                              0.59    0.54                                             CONVERSION (Vol. %)  54.72   58.54                                            BENZENE SEL. %.sup.3 6.73    6.55                                             LIGHTS SEL. %.sup.3  15.16   8.34                                             MCP SEL. %           -3.81   12.72                                            ISO-C.sub.6 SEL. %.sup.3                                                                           68.28   71.95                                            HOURS ON STREAM      25.00   26.25                                            TEMPERATURE (°F.)                                                                           902     901                                              ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE 111-1                                                     ______________________________________                                        (Catalyst C (SAPO-5)).sup.1                                                   ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.00    0.00                                            ETHANE                0.27    0.15                                            PROPANE               2.42    1.94                                            ISOBUTANE             0.46    0.44                                            N-BUTANE              0.31    0.35                                            ISO-PENTANE           0.32    0.34                                            N-PENTANE             0.14    0.14                                            TOTAL LIGHTS (C.sub.5 -)                                                                            3.92    3.36                                            2,2 DIMETHYL BUTANE   0.10    0.09                                            2 METHYL PENTANE      4.63    4.52                                            3 METHYL PENTANE      6.64    6.62                                            N-HEXANE              73.51   73.80                                           METHYL CYCLOPENTANE (MCP)                                                                           10.28   10.59                                           CYCLOHEXANE           0.10    0.00                                            TOTAL C.sub.6 SATURATES                                                                             95.26   95.62                                           BENZENE               0.82    1.01                                            CALCULATIONS:                                                                 RON (CALCULATED)      36.27.sup.2                                                                           --.sup.2                                        VOLUME % YIELD        96.52.sup.2                                                                           --.sup.2                                        METHANE/PROPANE       0.00    0.00                                            ISO-BUTANE/N-BUTANE   1.48    1.26                                            ISO-PENTANE/N-PENTANE 2.27    2.40                                            CONVERSION (Vol. %)   14.88   14.54                                           BENZENE SEL. %.sup.3  5.52    6.97                                            LIGHTS SEL. %.sup.3   26.33   23.13                                           MCP SEL. %            3.93    6.17                                            ISO-C.sub.6 SEL. %.sup.3                                                                            50.58   50.09                                           HOURS ON STREAM       19.50   20.25                                           TEMPERATURE (°F.)                                                                            859     859                                             ______________________________________                                         .sup.1 Catalyst Weight: 0.354 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE III-2                                                     ______________________________________                                        (Catalyst C (SAPO-5)).sup.1                                                   ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE              0.09    0.11                                             ETHANE               0.42    0.46                                             PROPANE              3.29    3.16                                             ISOBUTANE            0.54    0.40                                             N-BUTANE             0.50    0.39                                             ISO-PENTANE          0.32    0.24                                             N-PENTANE            0.21    0.19                                             TOTAL LIGHTS (C.sub.5 -)                                                                           5.37    4.94                                             2,2 DIMETHYL BUTANE  0.17    0.12                                             2 METHYL PENTANE     5.53    4.96                                             3 METHYL PENTANE     7.42    6.96                                             N-HEXANE             70.41   70.81                                            METHYL CYCLOPENTANE  9.69    10.55                                            CYCLOHEXANE          0.23    0.22                                             TOTAL C.sub.6 SATURATES                                                                            93.45   93.62                                            BENZENE              1.18    1.44                                             CALCULATIONS:                                                                 RON (CALCULATED)     37.58.sup.2                                                                           --.sup.2                                         VOLUME % YIELD       94.91.sup.2                                                                           --.sup.2                                         METHANE/PROPANE      0.03    0.03                                             ISO-BUTANE/N-BUTANE  1.07    1.03                                             ISO-PENTANE/N-PENTANE                                                                              1.51    1.24                                             CONVERSION (Vol %)   18.47   18.01                                            BENZENE SEL. %.sup.3 6.37    7.98                                             LIGHTS SEL. %.sup.3  29.10   27.45                                            MCP SEL. %           -0.04   4.75                                             ISO-C.sub.6 SEL. %.sup.3                                                                           50.94   46.18                                            HOURS ON STREAM      22.00   24.25                                            TEMPERATURE (°F.)                                                                           901     900                                              ______________________________________                                         .sup.1 Catalyst Weight: 0.354 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 3

A catalyst according to the instant invention was prepared according tothe procedure employed in example 1(b) using a SAPO-11 prepared by aprocedure similar to that employed in example 1(b). The catalyst wasdenominated "Catalyst D" and evaluated according to the proceduredescribed in example 2. The results of this evaluation are set forth inTables IV-1 (860° F.) and IV-2 (900° F.) and are graphically depicted inFIGS. 1 to 4. The performance of Catalyst D is similar to that ofCatalyst B. The products obtained by use of Catalyst D show improvementin the product distribution and improvement in the calculated RON of theproducts when compared to that observed by use of Reference Catalyst A.

                  TABLE IV-1                                                      ______________________________________                                        (Catalyst (D SAPO-11)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.00    0.00                                            ETHANE                0.14    0.15                                            PROPANE               2.28    2.51                                            ISOBUTANE             0.11    0.13                                            N-BUTANE              0.21    0.22                                            ISO-PENTANE           0.15    0.15                                            N-PENTANE             0.10    0.11                                            TOTAL LIGHTS (C.sub.5 -)                                                                            2.99    3.27                                            2,2 DIMETHYL BUTANE   0.55    0.69                                            2 METHYL PENTANE      19.35   19.73                                           3 METHYL PENTANE      15.22   15.48                                           N-HEXANE              49.71   48.25                                           METHYL CYCLOPENTANE (MCP)                                                                           8.67    8.36                                            CYCLOHEXANE           0.15    0.44                                            TOTAL C.sub.6 SATURATES                                                                             93.64   92.95                                           BENZENE               3.37    3.77                                            CALCULATIONS:                                                                 RON (CALCULATED)      53.05.sup.2                                                                           --.sup.2                                        VOLUME % YIELD        96.46.sup.2                                                                           --.sup.2                                        METHANE/PROPANE       0.00    0.00                                            ISO-BUTANE/N-BUTANE   0.53    0.57                                            ISO-PENTANE/N-PENTANE 1.53    1.37                                            CONVERSION (Vol. %)   42.44   44.13                                           BENZENE SEL. %.sup.3  7.93    8.55                                            LIGHTS SEL. %.sup.3   7.05    7.42                                            MCP SEL. %            -2.42   -3.02                                           ISO-C.sub.6 SEL. %.sup.3                                                                            73.79   73.41                                           HOURS ON STREAM       20.50   21.50                                           TEMPERATURE (°F.)                                                                            860     865                                             ______________________________________                                         .sup.1 Catalyst Weight: 0.340 grams.                                          .sup.2 Average value of samples.                                              .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE IV-2                                                      ______________________________________                                        (Catalyst D (SAPO-11)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.08    0.07                                            ETHANE                0.28    0.27                                            PROPANE               4.00    3.85                                            ISOBUTANE             0.17    0.16                                            N-BUTANE              0.46    0.37                                            ISO-PENTANE           0.22    0.16                                            N-PENTANE             0.20    0.16                                            TOTAL LIGHTS (C.sub.5 -)                                                                            5.39    5.02                                            2,2 DIMETHYL BUTANE   0.77    0.74                                            2 METHYL PENTANE      17.93   17.57                                           3 METHYL PENTANE      14.79   14.55                                           N-HEXANE              48.74   49.80                                           METHYL CYCLOPENTANE (MCP)                                                                           8.12    8.47                                            CYCLOHEXANE           0.16    0.34                                            TOTAL C.sub.6 SATURATES                                                                             90.51   91.46                                           BENZENE               4.10    3.52                                            CALCULATIONS:                                                                 RON (CALCULATED)      52.79.sup.2                                                                           --.sup.2                                        VOLUME % YIELD        94.13.sup.2                                                                           --.sup.2                                        METHANE/PROPANE       0.02    0.02                                            ISO-BUTANE/N-BUTANE   0.37    0.43                                            ISO-PENTANE/N-PENTANE 1.12    1.00                                            CONVERSION (Vol. %)   43.56   42.34                                           BENZENE SEL. %.sup.3  9.42    8.31                                            LIGHTS SEL. %.sup.3   12.38   11.87                                           MCP SEL. %            -3.62   -2.89                                           ISO-C.sub.6 SEL %.sup.3                                                                             68.18   69.08                                           HOURS ON STREAM       24.25   26.00                                           TEMPERATURE (°F.)                                                                            900     902                                             ______________________________________                                         .sup.1 Catalyst Weight: 0.340 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 4

A Reference Catalyst E was prepared to contain 0.52 weight percentchloride. This catalyst contained a higher chloride content thanReference Catalyst A of example 1. Reference Catalyst E was preparedsimilar to Catalyst A using an alumina carrier, except ReferenceCatalyst E did not contain a silica binder as was employed in ReferenceCatalyst A. Reference Catalyst E was prepared by mixing 17.6 grams of analumina (CATAPAL) with 1.8 grams of concentrated nitric acid and 26.4grams of distilled water. The peptized alumina was mixed with 75.8 gramsof a calcined alumina (CATAPAL) (calcined at 540° C. in air for 16 hoursto an LOI (Loss On Ignition) of 1.4 weight percent to form a gammaalumina). The mixture was then extruded into 1/16-inch extrudates anddried overnight in air at 110° C. The extrudates were then calcined at540° C. for 3 hours. The calcined extrudates had a pore volume of 67.5milliliter per gram and were pore filled with 0.560 grams of H₂ PtCl₆ in0.77 grams of concentrated HCl in water. The resulting product was driedovernight in air at 110° C. and calcined in air at 540° C. for 3 hours.The catalyst was denominated Reference "Catalyst E". Catalyst E wasevaluated according to the procedures employed for Catalyst A in Example2. The results of this evaluation are set forth in Table V-1 to V-2 andare graphically depicted in FIGS. 1 to 4. Reference Catalyst E gavesimilar selectivity with higher activity (as a result of the higherchloride content) than Reference Catalyst A.

                  TABLE V-1                                                       ______________________________________                                        (Reference Catalyst E).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               1.30    1.03                                            ETHANE                1.63    1.30                                            PROPANE               2.83    2.31                                            ISOBUTANE             0.60    0.52                                            N-BUTANE              1.99    1.70                                            ISO-PENTANE           0.86    0.74                                            N-PENTANE             2.17    1.94                                            TOTAL LIGHTS (C.sub.5 -)                                                                            11.38   9.53                                            2,2 DIMETHYL BUTANE   3.10    2.99                                            2 METHYL PENTANE      20.94   20.97                                           3 METHYL PENTANE      14.44   14.90                                           N-HEXANE              42.16   43.49                                           METHYL CYCLOPENTANE (MCP)                                                                           3.10    3.04                                            CYCLOHEXANE           0.00    0.00                                            TOTAL C.sub.6 SATURATES                                                                             83.74   85.38                                           BENZENE               4.89    5.08                                            CALCULATIONS:                                                                 RON (CALCULATED)      54.64.sup.2                                                                           --.sup.2                                        VOLUME % YIELD        92.22.sup.2                                                                           --.sup.2                                        METHANE/PROPANE       0.46    0.44                                            ISO-BUTANE/N-BUTANE   0.30    0.31                                            ISO-PENTANE/N-PENTANE 0.40    0.38                                            CONVERSION (Vol. %)   51.18   49.64                                           BENZENE SEL. %.sup.3  9.55    10.24                                           LIGHTS SEL. %.sup.3   22.23   19.21                                           MCP SEL. %            -12.88  -13.41                                          ISO-C.sub.6 SEL. %.sup.3                                                                            67.47   70.33                                           HOURS ON STREAM       20.75   21.50                                           TEMPERATURE (°F.)                                                                            860     861                                             ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE V-2                                                       ______________________________________                                        (Reference Catalyst E).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               1.87      1.67                                          ETHANE                2.56      2.31                                          PROPANE               4.00      3.56                                          ISOBUTANE             1.50      1.38                                          BUTANE                2.83      2.49                                          ISO-PENTANE           1.96      1.80                                          N-PENTANE             2.72      2.58                                          TOTAL LIGHTS (C.sub.5 --)                                                                           17.44     15.79                                         2,2 DIMETHYL BUTANE   4.83      4.88                                          2 METHYL PENTANE      22.19     22.72                                         3 METHYL PENTANE      14.92     15.57                                         N-HEXANE              28.84     30.18                                         METHYL CYCLOPENTANTE (MCP)                                                                          2.73      2.72                                          CYCLOHEXANE           0.00      0.00                                          TOTAL C.sub.6 SATURATES                                                                             73.52     76.07                                         BENZENE               9.04      8.14                                          CALCULATIONS:                                                                 RON (CALCULATED)      63.47.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        86.97.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.47      0.47                                          ISO-BUTANE/N-BUTANE   0.53      0.55                                          ISO-PENTANE/N-PENTANE 0.72      0.70                                          CONVERSION (Vol. %)   66.60     65.05                                         BENZENE SEL. %3       13.57     12.52                                         LIGHTS SEL. %.sup.3   26.19     24.27                                         MCP SEL. %            -10.45    -10.72                                        ISO-C.sub.6 SEL. %.sup.3                                                                            57.05     60.29                                         HOURS ON STREAM       24.00     25.00                                         TEMPERATURE (°F.)                                                                            901       900                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 5

A catalyst was prepared using a Pt/Cl-alumina component prepared in asimilar manner to Reference Catalyst A of example 1(a) and by using aSAPO-11 prepared according to the procedure described in example 1(b).The SAPO-11 product contained essentially no impurity phases as a resultof its preparation. As above mentioned, the Pt/Cl-alumina was asprepared as in example 1(a), except the Pt/Cl-alumina component wascalcined at 500° C. (instead of 260° C.) for 2 hours in air prior toadmixture with the SAPO-11 and silica. The catalyst (denominated as"Catalyst F") was prepared similar to Catalyst B. Catalyst F wasevaluated according to the procedure described in Example 2. The resultsof this evaluation are reported in Tables VI-1 (860° F.) and VI-2 (900°F.) and are graphically depicted in FIGS. 1 to 4. Comparison of theresults for Catalyst F and Reference Catalysts A and E show theimprovement in the calculated RON of products obtained by use ofCatalyst F.

                  TABLE VI-1                                                      ______________________________________                                        (CATALYST F (SAPO-11)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.11      0.10                                          ETHANE                0.25      0.23                                          PROPANE               2.76      2.67                                          ISOBUTANE             0.13      0.14                                          N-BUTANE              0.32      0.34                                          ISO-PENTANE           0.21      0.19                                          N-PENTANE             0.22      0.19                                          TOTAL LIGHTS (C.sub.5 --)                                                                           4.00      3.86                                          2,2 DIMETHYL BUTANE   1.43      1.37                                          2 METHYL PENTANE      27.18     26.55                                         3 METHYL PENTANE      19.90     19.76                                         N-HEXANE              36.50     36.98                                         METHYL CYCLOPENTANE (MCP)                                                                           5.65      5.98                                          CYCLOHEXANE           0.08      0.08                                          TOTAL C.sub.6 SATURATES                                                                             90.73     90.73                                         BENZENE               5.27      5.41                                          CALCULATIONS:                                                                 RON (CALCULATED)      60.86.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        95.78.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.04      0.04                                          ISO-BUTANE/N-BUTANE   0.40      0.42                                          ISO-PENTANE/N-PENTANE 0.97      0.97                                          CONVERSION (Vol. %)   57.74     57.18                                         BENZENE SEL. %.sup.3  9.13      9.47                                          LIGHTS SEL. %.sup.3   6.93      6.75                                          MCP SEL. %            -7.00     -6.49                                         ISO-C.sub.6 SEL. %.sup.3                                                                            77.31     76.64                                         HOURS ON STREAM       20.00     21.25                                         TEMPERATURE (°F.)                                                                            858       860                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE VI-2                                                      ______________________________________                                        (CATALYST F (SAPO-11)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.20      0.19                                          ETHANE                0.48      0.48                                          PROPANE               4.37      4.43                                          ISOBUTANE             0.31      0.31                                          N-BUTANE              0.53      0.55                                          ISO-PENTANE           0.32      0.34                                          N-PENTANE             0.33      0.33                                          TOTAL LIGHTS (C.sub.5 --)                                                                           6.53      6.63                                          2,2 DIMETHYL BUTANE   2.35      2.24                                          2 METHYL PENTANE      27.07     26.73                                         3 METHYL PENTANE      19.88     19.57                                         N-HEXANE              32.73     33.59                                         METHYL CYCLOPENTANE (MCP)                                                                           4.47      4.40                                          CYCLOHEXANE           0.07      0.04                                          TOTAL C.sub.6 SATURATES                                                                             86.56     86.57                                         BENZENE               6.90      6.80                                          CALCULATIONS:                                                                 RON (CALCULATED)      62.65.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        93.18.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.05      0.04                                          ISO-BUTANE/N-BUTANE   0.58      0.55                                          ISO-PENTANE/N-PENTANE 0.96      1.02                                          CONVERSION (Vol. %)   62.09     61.10                                         BENZENE SEL. %.sup.3  11.12     11.12                                         LIGHTS SEL. %.sup.3   10.52     10.85                                         MCP SEL. %            -8.41     -8.67                                         ISO-C.sub.6 SEL. %.sup.3                                                                            77.13     73.05                                         HOURS ON STREAM       23.50     25.25                                         TEMPERATURE (°F.)                                                                            900       901                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 6

A catalyst (denominated "Catalyst G") was prepared according to thisinvention according to the procedure employed to prepare Catalyst B inexample 1, except the Pt/Cl-alumina component was as prepared in example1(a), except it was calcined at 540° C. (instead of 260° C.) for 2 hoursand SAPO-41 was employed instead of SAPO-11. SAPO-41 was producedaccording to the general procedures set forth in U.S. Pat. No.4,440,871. A reaction mixture was prepared using Kaiser-SAT alumina 70wt. % Al₂ O₃, 30 wt. % H₂ O), 85 wt. % H₃ PO₄, CAB-O-SILT EH-5 (93.2 wt.% SiO₂, 6.9 wt. % H₂ O), di-n-propylamine (Pr₂ NH) and water. Thereaction mixture was heated to 200° C. without stirring and held at 200°C. without stirring for 48 hours. A SAPO-41 product was obtained.Chemical analysis of the SAPO-41 product gave the following

    ______________________________________                                        Weight Percent                                                                ______________________________________                                        Al.sub.2 O.sub.3   34.9                                                       P.sub.2 O.sub.5    43.0                                                       SiO.sub.2          10.6                                                       Carbon             5.5                                                        Nitrogen           1.1                                                        LOI (Loss On Ignition)                                                                           11.4                                                       ______________________________________                                    

The product was calcined at above 450° C. in air to remove organictemplating agent.

Catalyst G was evaluated according to the procedure described in example2 at process temperatures of 860° F. and 900° F. Comparison of theproducts obtained by use of Catalyst G and Catalyst E show that CatalystG is more active and more selective to higher octane products thanproducts obtained using Reference Catalysts A and E. The results of thisevaluation are set forth in Tables VII-1 and VII-2 and are graphicallydepicted in FIGS. 1 to 4.

                  TABLE VII-1                                                     ______________________________________                                        (CATALYST G (SAPO-41)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.12      0.12                                          ETHANE                0.41      0.43                                          PROPANE               3.36      3.52                                          ISOBUTANE             0.21      0.25                                          N-BUTANE              0.50      0.54                                          ISO-PENTANE           0.14      0.16                                          N-PENTANE             0.21      0.20                                          TOTAL LIGHTS (C.sub.5 --)                                                                           4.95      5.22                                          2,2 DIMETHYL BUTANE   1.04      0.99                                          2 METHYL PENTANE      22.89     22.27                                         3 METHYL PENTANE      17.36     16.87                                         N-HEXANE              42.83     44.09                                         METHYL CYCLOPENTANE (MCP)                                                                           6.95      6.97                                          CYCLOHEXANE           0.04      0.10                                          TOTAL C.sub.6 SATURATES                                                                             91.11     91.29                                         BENZENE               3.93      3.49                                          CALCULATIONS:                                                                 RON (CALCULATED)      55.97.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        94.79.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.04      0.03                                          ISO-BUTANE/N-BUTANE   0.42      0.46                                          ISO-PENTANE/N-PENTANE 0.69      0.79                                          CONVERSION (Vol. %)   50.40     48.95                                         BENZENE SEL. %.sup.3  7.80      7.14                                          LIGHTS SEL. %.sup.3   9.83      10.66                                         MCP SEL. %            -5.45     -5.56                                         ISO-C.sub.6 SEL. %.sup.3                                                                            74.17     74.12                                         HOURS ON STREAM       20.00     21.00                                         TEMPERATURE (°F.)                                                                            862       862                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE VII-2                                                     ______________________________________                                        (CATALYST G (SAPO-41)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.18      0.18                                          ETHANE                0.59      0.61                                          PROPANE               4.48      4.64                                          ISOBUTANE             0.31      0.32                                          N-BUTANE              0.72      0.71                                          ISO-PENTANE           0.23      0.22                                          N-PENTANE             0.33      0.28                                          TOTAL LIGHTS (C.sub.5 --)                                                                           6.84      6.96                                          2,2 DIMETHYL BUTANE   1.62      1.46                                          2 METHYL PENTANE      23.87     23.39                                         3 METHYL PENTANE      17.99     17.71                                         N-HEXANE              38.62     39.98                                         METHYL CYCLOPENTANE (MCP)                                                                           5.84      5.98                                          CYCLOHEXANE           0.10      0.04                                          TOTAL C.sub.6 SATURATES                                                                             88.04     88.56                                         BENZENE               5.12      4.48                                          CALCULATIONS:                                                                 RON (CALCULATED)      58.30.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        93.02.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.04      0.04                                          ISO-BUTANE/N-BUTANE   0.43      0.45                                          ISO-PENTANE/N-PENTANE 0.71      0.77                                          CONVERSION (Vol. %)   57.28     53.70                                         BENZENE SEL. %.sup.3  9.26      8.35                                          LIGHTS SEL. %.sup.3   12.37     12.96                                         MCP SEL. %            -6.98     -6.92                                         ISO-C.sub.6 SEL. %.sup.3                                                                            71.70     71.98                                         HOURS ON STREAM       24.75     25.75                                         TEMPERATURE (°F.)                                                                            901       900                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 7

A second sample from the preparation of Catalyst G, as described inexample 6, was evaluated as a reforming catalyst as described in example6 using the procedure described in example 2. The results of thisevaluation were similar to those set forth in example 6 and are setforth in Tables VIII-1 (860° F.) and VIII-2 (900° F.).

                  TABLE VIII-1                                                    ______________________________________                                        (CATALYST G (SAPO-41)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.13      0.13                                          ETHANE                0.40      0.40                                          PROPANE               3.36      3.37                                          ISOBUTANE             0.10      0.14                                          N-BUTANE              0.46      0.56                                          ISO-PENTANE           0.12      0.15                                          N-PENTANE             0.17      0.24                                          TOTAL LIGHTS (C.sub.5 --)                                                                           4.74      4.98                                          2,2 DIMETHYL BUTANE   0.81      0.91                                          2 METHYL PENTANE      22.40     22.73                                         3 METHYL PENTANE      16.72     16.85                                         N-HEXANE              44.45     44.03                                         METHYL CYCLOPENTANE (MCP)                                                                           7.01      6.81                                          CYCLOHEXANE           0.15      0.16                                          TOTAL C.sub.6 SATURATES                                                                             91.55     91.48                                         BENZENE               3.71      3.54                                          CALCULATIONS:                                                                 RON (CALCULATED)      55.48.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        95.02.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.04      0.04                                          ISO-BUTANE/N-BUTANE   0.23      0.25                                          ISO-PENTANE/N-PENTANE 0.71      0.64                                          CONVERSION (Vol. %)   48.52     49.02                                         BENZENE SEL. %.sup.3  7.65      7.22                                          LIGHTS SEL. %.sup.3   9.77      10.15                                         MCP SEL. %            -5.52     -5.89                                         ISO-C.sub.6 SEL. %.sup.3                                                                            74.47     74.87                                         HOURS ON STREAM       22.00     22.50                                         TEMPERATURE (°F.)                                                                            859       861                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE VIII-2                                                    ______________________________________                                        (SAPO-41)).sup.1                                                              ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE                0.22                                                   ETHANE                 0.66                                                   PROPANE                4.85                                                   ISOBUTANE              0.24                                                   N-BUTANE               0.72                                                   ISO-PENTANE            0.30                                                   N-PENTANE              0.33                                                   TOTAL LIGHTS (C.sub.5 --)                                                                            7.32                                                   2,2 DIMETHYL BUTANE    1.49                                                   2 METHYL PENTANE       23.58                                                  3 METHYL PENTANE       17.55                                                  N-HEXANE               38.83                                                  METHYL CYCLOPENTANE (MCP)                                                                            5.83                                                   CYCLOHEXANE            0.15                                                   TOTAL C.sub.6 SATURATES                                                                              87.43                                                  BENZENE                5.25                                                   CALCULATIONS:                                                                 RON (CALCULATED)       58.57                                                  VOLUME % YIELD         92.58                                                  METHANE/PROPANE        0.05                                                   ISO-BUTANE/N-BUTANE    0.33                                                   ISO-PENTANE/N-PENTANE  0.91                                                   CONVERSION (Vol %)     55.04                                                  BENZENE SEL. %         9.54                                                   LIGHTS SEL. %          13.30                                                  MCP SEL. %             -7.01                                                  ISO-C.sub.6 SEL. %     70.54                                                  HOURS ON STREAM        26.25                                                  TEMPERATURE (°F.)                                                                             900                                                    ______________________________________                                         .sup.1 Catalyst Weight: 0.3500 grams.                                    

EXAMPLE 8

A catalyst (denominated "Catalyst H") was prepared similar to Catalyst Gin example 6, except the SAPO-41 was prepared from a reaction mixturehaving different molar oxide ratios. The reaction mixture was heated to200° C. without stirring and held at 200° C. without stirring for 24hours. A SAPO-41 product was obtained. Chemical analysis of the SAPO-41product gave the following

    ______________________________________                                        Al.sub.2 O.sub.3   39.5                                                       P.sub.2 O.sub.5    39.6                                                       SiO.sub.2          8.4                                                        Carbon             4.8                                                        Nitrogen           0.9                                                        LOI (Loss On Ignition)                                                                           12.4                                                       ______________________________________                                    

Catalyst H was evaluated according to the procedure described in example2 and the results are set forth in Tables IX-1 (860° F.) and IX-2 (900°F.) and are graphically depicted in FIGS. 1 to 4. These results aresimilar to those obtained in examples 6 and 7 and demonstrate thebenefits of a catalyst containing SAPO-41 over a similar referencecatalyst without SAPO-41.

                  TABLE IX-1                                                      ______________________________________                                        (CATALYST H (SAPO-41)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE               0.08      0.09                                          ETHANE                0.25      0.30                                          PROPANE               2.84      3.20                                          ISOBUTANE             0.08      0.08                                          N-BUTANE              0.33      0.37                                          ISO-PENTANE           0.10      0.08                                          N-PENTANE             0.16      0.14                                          TOTAL LIGHTS (C.sub.5 --)                                                                           3.84      4.27                                          2,2 DIMETHYL BUTANE   0.63      0.69                                          2 METHYL PENTANE      21.69     23.43                                         3 METHYL PENTANE      16.69     17.88                                         N-HEXANE              45.58     42.66                                         METHYL CYCLOPENTANE (MCP)                                                                           8.16      7.93                                          CYCLOHEXANE           0.13      0.12                                          TOTAL C.sub.6 SATURATES                                                                             92.87     92.71                                         BENZENE               3.30      3.02                                          CALCULATIONS:                                                                 RON (CALCULATED)      55.95.sup.2                                                                             --.sup.2                                      VOLUME % YIELD        95.71.sup.2                                                                             --.sup.2                                      METHANE/PROPANE       0.03      0.03                                          ISO-BUTANE/N-BUTANE   0.24      0.22                                          ISO-PENTANE/N-PENTANE 0.65      0.59                                          CONVERSION (Vol. %)   47.22     50.60                                         BENZENE SEL. %.sup.3  6.98      5.97                                          LIGHTS SEL. %.sup.3   8.12      8.43                                          MCP SEL. %            -3.25     -3.49                                         ISO-C.sub.6 SEL. %.sup.3                                                                            74.51     75.45                                         HOURS ON STREAM       20.00     21.00                                         TEMPERATURE (°F.)                                                                            859       860                                           ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE IX-2                                                      ______________________________________                                        (CATALYST H (SAPO-41)).sup.1                                                  ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE                0.17    0.16                                           ETHANE                 0.58    0.51                                           PROPANE                5.10    4.80                                           ISOBUTANE              0.31    0.21                                           N-BUTANE               0.74    0.60                                           ISO-PENTANE            0.21    0.18                                           N-PENTANE              0.24    0.23                                           TOTAL UGHTS (C.sub.5 -)                                                                              7.34    6.69                                           2,2 DIMETHYL BUTANE    1.29    1.14                                           2 METHYL PENTANE       23.40   22.70                                          3 METHYL PENTANE       18.12   17.29                                          N-HEXANE               38.59   40.43                                          METHYL CYCLOPENTANE (MCP)                                                                            6.73    6.77                                           CYCLOHEXANE            0.16    0.13                                           TOTAL C.sub.6 SATURATES                                                                              88.30   88.45                                          BENZENE                                                                       CALCULATIONS:                                                                 RON (CALCULATED)       58.24.sup.2                                                                           -.sup.2                                        VOLUME % YIELD         92.72.sup.2                                                                           -.sup.2                                        METHANE/PROPANE        0.03    0.03                                           ISO-BUTANE/N-BUTANE    0.42    0.34                                           ISO-PENTANE/N-PENTANE  0.85    0.79                                           CONVERSION (Vol. %)    55.31   53.18                                          BENZENE SEL %.sup.3    7.88    9.13                                           LIGHTS SEL %.sup.3     13.28   12.58                                          MCP SEL %.sup.3        -5.35   -5.50                                          ISO-C.sub.6 SEL %.sup.3                                                                              70.55   50.15                                          HOURS ON STREAM        24.50   26.50                                          TEMPERATURE (°F.)                                                                             900     900                                            ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 9

A comparative catalyst (denominated "Catalyst I") was prepared employingthe preparative procedure employed for Catalyst B in example 1, exceptSAPO-34 was substituted for SAPO-11. The preparation of SAPO-34 isdescribed in examples 32 to 38 of U.S. Pat. No. 4,440,871, incorporatedherein by reference. SAPO-34 is a small pore silicoaluminophosphate andis not characterized by the adsorption characteristics for isobutanecharacteristic of the MP-SAPOs employed in the catalysts and processesof the instant invention.

Catalyst I was evaluated according to the procedure described in example2, above. The results of this evaluation are set forth in Tables X-1(860° F.) and X-2 (900° F.) and are graphically depicted in FIGS. 1 to4. Catalyst I gave products having iso C₆ 's/light and benzene/lightsratios less than that obtained by use of Reference Catalyst A. Inaddition, the plot of Volume % Yield vs. RON (calculated) in FIG. 3shows Catalyst I was inferior to Reference Catalyst A and to catalystscontaining SAPO-11 and SAPO-41.

                  TABLE X-1                                                       ______________________________________                                        (COMPARATIVE CATALYST I (SAPO-34)).sup.1                                      ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE                0.14    0.13                                           ETHANE                 1.01    0.94                                           PROPANE                14.31   13.07                                          ISOBUTANE              0.04    0.04                                           N-BUTANE               1.69    1.59                                           ISO-PENTANE            0.07    0.07                                           N-PENTANE              0.57    0.51                                           TOTAL LIGHTS (C.sub.5 -)                                                                             17.83   16.35                                          2,2 DIMETHYL BUTANE    0.27    0.28                                           2 METHYL PENTANE       10.54   10.11                                          3 METHYL PENTANE       8.94    8.83                                           N-HEXANE               51.43   52.92                                          METHYL CYCLOPENTANE (MCP)                                                                            8.75    9.08                                           CYCLOHEXANE            0.04    0.10                                           TOTAL C.sub.6 SATURATES                                                                              79.98   81.32                                          BENZENE                2.19    2.33                                           CALCULATIONS:                                                                 RON (CALCULATED)       45.142.sup.                                                                           -.sup.2                                        VOLUME % YIELD         82.96   -.sup.2                                        METHANE/PROPANE        0.01    0.01                                           ISO-BUTANE/N-BUTANE    0.02    0.03                                           ISO-PENTANE/N-PENTANE  0.12    0.13                                           CONVERSION (Vol. %)    40.45   38.72                                          BENZENE SEL. %.sup.3   5.42    6.02                                           LJGHTS SEL. %.sup.3    44.08   42.22                                          MCP SEL.%              -2.33   -1.59                                          ISO-C.sub.6 SEL. %.sup.3                                                                             39.19   39.70                                          HOURS ON STREAM        19.75   21.00                                          TEMPERATURE (°F.)                                                                             861     862                                            ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE X-2                                                       ______________________________________                                        (Comparative Catalyst I (SAPO-34)).sup.1                                      ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE                0.22    0.20                                           ETHANE                 1.39    1.29                                           PROPANE                13.71   11.66                                          ISOBUTANE              0.12    0.15                                           N-BUTANE               1.88    1.89                                           ISO-PENTANE            0.12    0.16                                           N-PENTANE              0.58    0.54                                           TOTAL LIGHTS (C.sub.5 -)                                                                             8.01    15.90                                          2,2 DIMETHYL BUTANE    0.54    0.49                                           2 METHYL PENTANE       12.51   12.30                                          3 METHYL PENTANE       10.29   10.38                                          N-HEXANE               47.58   49.02                                          METHYL CYCLOPENTANE (MCP)                                                                            7.68    8.08                                           CYCLOHEXANE            0.09    0.08                                           TOTAL C.sub.6 SATURATES                                                                              78.69   80.35                                          BENZENE                3.29    3.75                                           CALCULATIONS:                                                                 RON (CALCULATED)       48.19.sup.2                                                                           -.sup.2                                        VOLUME % YIELD         83.01.sup.2                                                                           -.sup.2                                        METHANE/PROPANE        0.02    0.02                                           ISO-BUTANE/N-BUTANE    0.07    0.08                                           ISO-PENTANE/N-PENTANE  0.21    0.29                                           CONVERSION (Vol. %)    44.90   43.24                                          BENZENE SEL. %.sup.3   7.34    8.67                                           LIGHTS SEL. %          40.12   36.78                                          MCP SEL. %             -4.48   -3.73                                          ISO-C.sub.6 SEL. %.sup.3                                                                             43.39   44.63                                          HOURS ON STREAM        24.50   25.75                                          TEMPERATURE (°F.)                                                                             899     900                                            ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 10

A comparative catalyst (denominated "Catalyst J") was prepared similarto the preparation of Catalyst B in Example 1, above, except silicalitewas substituted for SAPO-11. Silicalite and its preparation aredisclosed in U.S. Pat. No. 4,061,724, incorporated herein by reference.Silicalite is a crystalline silica material having a characteristicadsorption for isobutane and triethylamine within the adsorptioncriteria described for MP-SAPO. Silicalite has a pore size of about 6Angstroms.

Catalyst J was evaluated according to the procedure described in example2 and the results of that evaluation are set forth in Tables XI-1 (860°F.) and XI-2 (900° F.) and are graphically depicted in FIGS. 1, 2 and 4.The results of the evaluation show that, although silicalite ischaracterized by adsorption criteria similar to MP-NZMSs, silicalitedoes not provide the benefits provided by catalysts containingMP-NZMS(s), as indicated by the large yield losses associated with useof the silicalite- containing Catalyst J.

                  TABLE XI-1                                                      ______________________________________                                        (COMPARATIVE CATALYST J (Silicalite)).sup.1                                   ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE                0.33    0.35                                           ETHANE                 3.57    3.81                                           PROPANE                27.92   27.76                                          ISOBUTANE              2.51    2.66                                           N-BUTANE               7.37    7.39                                           ISO-PENTANE            2.06    1.94                                           N-PENTANE              2.58    2.48                                           TOTAL LIGHTS (C.sub.5 -)                                                                             46.34   46.39                                          2,2 DIMETHYL BUTANE    0.79    0.77                                           2 METHYL PENTANE       14.03   14.51                                          3 METHYL PENTANE       10.32   10.68                                          N-HEXANE               21.06   19.65                                          METHYL CYCLOPENTANE (MCP)                                                                            3.10    3.00                                           CYCLOHEXANE            0.11    0.09                                           TOTAL C.sub.6 SATURATES                                                                              49.40   48.71                                          BENZENE                4.26    4.90                                           CALCULATIONS:                                                                 RON (CALCULATED)       62.55.sup.2                                                                           -.sup.2                                        VOLUME % YIELD         57.69.sup.2                                                                           -.sup.2                                        METHANE/PROPANE        0.01    0.01                                           ISO-BUTANE/N-BUTANE    0.34    0.36                                           ISO-PENTANE/N-PENTANE  0.80    0.79                                           CONVERSION (Vol. %)    75.62   77.25                                          BENZENE SEL.%.sup.3    5.63    6.35                                           LIGHTS SEL.%.sup.3     61.29   60.05                                          MCP SEL. %             -8.72   -8.66                                          ISO-C.sub.6 SEL. %.sup.3                                                                             28.16   28.62                                          HOURS ON STREAM        19.75   22.00                                          TEMPERATURE (°F.)                                                                             861     861                                            ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

                  TABLE XI-2                                                      ______________________________________                                        (COMPARATIVE CATALYST J (Silicalite)).sup.1                                   ______________________________________                                        GC PRODUCT ANALYSIS (WEIGHT PERCENT):                                         METHANE                0.62    0.69                                           ETHANE                 5.37    6.38                                           PROPANE                40.12   37.10                                          ISOBUTANE              3.42    3.79                                           N-BUTANE               8.68    9.46                                           ISO-PENTANE            1.96    1.93                                           N-PENTANE              2.01    2.23                                           TOTAL LIGHTS (C.sub.5 -)                                                                             62.16   61.58                                          2,2 DIMETHYL BUTANE    0.92    0.76                                           2 METHYL PENTANE       11.01   10.28                                          3 METHYL PENTANE       7.73    7.66                                           N-HEXANE               11.32   11.69                                          METHYL CYCLOPENTANE (MCP)                                                                            1.53    1.62                                           CYCLOHEXANE            0.07    0.08                                           TOTAL C.sub.6 SATURATES                                                                              32.57   32.10                                          BENZENE                5.26    6.32                                           CALCULATIONS:                                                                 RON (CALCULATED)       67.90.sup.2                                                                           -.sup.2                                        VOLUME % YIELD         41.36.sup.2                                                                           -.sup.2                                        METHANE/PROPANE        0.02    0.02                                           ISO-BUTANE/N-BUTANE    0.39    0.40                                           ISO-PENTANE/N-PENTANE  0.97    0.86                                           CONVERSION (Vol. %)    86.89   86.47                                          BENZENE SEL. %.sup.3   6.06    7.31                                           LIGHTS SEL. %.sup.3    71.54   71.22                                          MCP SEL. %             -9.40   -9.33                                          ISO-C.sub.6 SEL. %.sup.3                                                                             18.16   17.16                                          HOURS ON STREAM        25.00   25.75                                          TEMPERATURE (°F.)                                                                             901     899                                            ______________________________________                                         .sup.1 Catalyst Weight: 0.350 grams.                                          .sup.2 Average value of both samples.                                         .sup.3 FIGS. 1 & 2 use average values of both samples.                   

EXAMPLE 11

A Commercial Reforming Catalyst (Commercial Reference Catalyst K) wasevaluated and compared with a catalyst containing the same commercialreforming catalyst in admixture with a SAPO-11 component. The commercialreforming catalyst comprised a Group VIII metal on chlorinated-aluminacatalyst typical of the Group VIII, chlorinated-alumina catalystsemployed in commercial reforming processes. The commercial reformingcatalyst was ground to form 20-40 mesh (U.S. Standard) particles andthen calcined in air at 480° C. for 2 hours. This catalyst wasdenominated Reference "Catalyst K".

A catalyst according to the instant invention was prepared by employingReference Catalyst K and a silica-bonded SAPO-11 component. The SAPO-11component was prepared as set forth in example 17 of U.S. Pat. No.4,440,871, except the digestion time was 40 hours. The SAPO-11 wascalcined and blended with a silica sol (LUDOX™), extruded, dried andcalcined in air, as described in part b) of example 1. TheSAPO-11/silica component was prepared to contain 87 weight percentSAPO-11 and 13 weight percent SiO₂, expressed on an anhydrous basis. Thecalcined SAPO-11/silica extrudates were ground to a 20-40 mesh (U.S.Standard). A catalyst according to the instant invention was prepared byforming a physical mixture containing 90 weight percent of commercialreforming Catalyst K and 10 weight percent of the SAPO-11/silicacomponent (expressed as anhydrous weight percents). The catalyst wasdenominated "Catalyst L" and contained 90 weight percent Catalyst K, 8.7wt % SAPO-11 and 1.3 wt % SiO₂.

Catalyst L and Reference Catalyst K were evaluated as reformingcatalysts with a naphtha feedstock having the followingcharacterization:

    ______________________________________                                        Aromatics*          15.6    Wt. %                                             Naphthenes*         24.5    Wt. %                                             Paraffins*          44.8    Wt. %                                             Unidentified Component(s)*                                                                        12.1    Wt. %                                             Average Molecular Wt.*                                                                            116.6   grams/mole                                        RON (Calculated)    47.2                                                      Calculated Density  0.7604                                                    ______________________________________                                         *Calculated by capillary gas chromatographic analysis of the individual       feedstock components                                                     

Each catalyst was tested by placing 8.6 grams of the 20-40 mesh catalystin a once through, tubular reactor having a bed length of about 4.5inches and an inside diameter of 0.43 inches. The reactor and catalystbed were purged with nitrogen and then with hydrogen at 1 atmosphere(zero (0) psig) and at a flow rate of 250 cc/min. The catalyst washeated from room temperature to 900° F. over a period of 3 to 4 hoursand then maintained at 900° F. for 1 hour with the hydrogen purge. Thecatalyst was then sulfided by increasing the hydrogen flow rate to 380cc/min and by adding hydrogen sulfide to the hydrogen stream at a rateof 20 cc/min. The hydrogen sulfide addition was continued for 10 minuteswhile the catalyst was maintained at 900° F. The reactor was then purgedfor 30 minutes with a hydrogen purge (380 cc/min). Each catalyst wasthen evaluated by heating the specific catalyst to the desired reactiontemperature. The reactor was pressurized to 200 psig and a feedstreamcontaining a 3 to 1 molar ratio of hydrogen to the naphtha feedstockintroduced to the reactor at 28 cc/hour (Weight Hourly SpaceVelocity=2.5). The liquid product was collected and analyzed bycapillary gas chromatographic procedures. The gas products weremonitored by dry test meters and analyzed by gas chromatographicprocedures. The liquid products analysis typically identified greaterthan 95 weight percent of the products. The acceptable product samplemixtures were determined by evaluating the mass balances for the sampleand by requiring a mass balance between the feedstock and products offrom greater than 99 percent to 101 percent by weight.

Catalysts K and L were evaluated and the RON and C₅ +Volume % Yieldcalculated, as above described. The evaluation of each catalyst wascarried out to provide a comparable Volume % Yield for each catalyst andto provide a mass balance greater than 99 percent to 101 percent byweight. This required the use of a lower reaction temperature for themore active Catalyst L (SAPO-11). Products were collected after about 65to 66 hours on stream and evaluated. The following results wereobtained:

    ______________________________________                                                  Commercial                                                                    Reference    SAPO-11-containing                                               Catalyst K   Catalyst L                                             ______________________________________                                        Temperature, °F.                                                                   940            921                                                Pressure, psig                                                                            200            200                                                H.sub.2 /Naphtha,                                                                         3.07           3.11                                               molar                                                                         WHSV        2.37           2.38                                               Mass Balance,                                                                             99.8           99.2                                               Wt. %                                                                         Time on Stream,                                                                           66.8           65.1                                               hours                                                                         Calculated  93.8           94.4                                               RON (C.sub.5 +)                                                               Calculated C.sub.5 +,                                                                     87.3           87.1                                               vol. %                                                                        ______________________________________                                    

The above results demonstrate that at comparable calculated RON and C₅+Vol. % Yield that Catalyst L was a more active catalyst than CatalystK. The increased activity of Catalyst K is indicated by the use of alower reaction temperature, 921° F., as compared to 940° C. forReference Catalyst K, to achieve similar calculated RON and C₅ +VolumeYield. The ability to employ a lower reaction temperature without aconcurrent loss in octane and/or yield is beneficial in both loweringthe overall cost of the reforming process and permits the processing oflarge feedstock volumes to produce products having comparable octane. Inaddition, the products produced by use of Catalyst L at the lowerprocess temperature and at a comparable C₅ +Vol. % Yield showed acomparable and even slightly higher calculated RON than the productsobtained by use of Commercial Reference Catalyst K.

EXAMPLE 12

A reforming catalyst of the prior art was prepared by oil-dropping aspherical alumina base according to the teachings of U.S. Pat. No.4,677,094 and impregnating platinum and rhenium. The chloride content ofthe catalyst was adjusted by stripping with wet air to effect a catalystcomposition as follows in wt. %:

    ______________________________________                                                 Pt  0.22                                                                      Re  0.44                                                                      Cl  0.2                                                              ______________________________________                                    

This catalyst is designated as the primary reforming catalyst. Thecatalyst was distributed in a pilot-plant reactor in three beds with thefollowing respective weight percentages:

    ______________________________________                                                Top bed 20                                                                    Middle bed                                                                            40                                                                    Bottom bed                                                                            40                                                            ______________________________________                                    

SAPO-11 was prepared in the manner of Example 1 (b), bound with 20% SiO₂and combined with the primary reforming catalyst in a weight ratio of 10SAPO-11 to 90 primary reforming catalyst to effect the followingcombinations:

Combination A: Homogeneous mixture of primary reforming catalyst andSAPO-11 throughout the three catalyst beds

Combination B: Primary reforming catalyst and SAPO-11 were mixed 65:35by weight in top catalyst bed.

Combination C: Primary reforming catalyst and SAPO-11 were mixed 78:22respectively by weight in middle catalyst bed.

Combination D: Primary reforming catalyst and SAPO-11 were mixed 78:22respectively by weight in bottom catalyst bed.

EXAMPLE 13

The four combinations of Example 12 were tested for catalytic reformingperformance at a pressure of 250 psig, 940° F., 2.5 liquid hourly spacevelocity and 6 molar hydrogen to hydrocarbon ratio. The feedstock usedfor the tests was a full-range naphtha, derived from a paraffinicmid-continent crude oil, having the following characteristics:

    ______________________________________                                        Specific gravity           0.746                                              Distillation, °C.:                                                                      IBP       86                                                                  50%       134                                                                 FBP       194                                                Volume %:        paraffins 60.8                                                                naphthenes                                                                              26.7                                                                aromatics 12.5                                               ______________________________________                                    

The favored location of SAPO-11 in the catalyst bed was determined bycomparing relative C₅ +product yields at 96.5 Research clear octanenumber for Combinations B, C, and D with those of Combination A on aweight % basis. The results were as follows:

    ______________________________________                                        Combination:     A      B        C    D                                       ______________________________________                                        Relative yield, mass %                                                                         base   -1.0     -0.2 +0.9                                    ______________________________________                                    

Placement of the SAPO-11 NZMS in the bottom, or last, catalyst bedclearly was favored according to the above results.

EXAMPLE 14

SAPO-11 and SAPO-5 prepared according to Example 1 (b) and (c),respectively, were characterized in order to contrast potential NZMScomponents of a reforming catalyst with respect to the parameters of theinvention. Adsorption capacities were measured on the calcined productusing a standard McBain-Baker gravimetric adsorption apparatus. Thefollowing data were obtained on samples activated at 350° F.:

    ______________________________________                                        Triethylamine                                                                             Pressure     Temp.,  Weight %                                     Adsorption  Torr         °C.                                                                            Adsorbed                                     ______________________________________                                        SAPO-11     2.65         22°                                                                            2.5                                          SAPO-5      2.65         22°                                                                            8.8                                          ______________________________________                                    

SAPO-11 also showed 4.5 wt. % isobutane adsorption at 500 Torr and 20°C. SAPO-11 thus represents a MP-NZMS of the invention, havingtriethylamine adsorption less than 5 wt. %, and even less than thepreferred value of 3 wt. %, in contrast to SAPO-5. Both SAPO-11 andSAPO-5 are microporous crystalline silicoaluminophosphates of U.S. PatNo. 4,440,871 (Lok et al.), wherein SAPO-11 is estimated to have a poresize of between 6.0 and 6.2 Å. The range of pore size of SAPO-5 was notdetermined in the '871 patent, but is shown as 7.3 Å in Meier, W. M. andOlson, D. H., Atlas of Zeolite Structure Types, 1987 Edition issued bythe Structure Commission of the International Zeolite Association. Theutility of the medium-pore SAPO-11 of the present invention is shown byhigher isohexane and benzene yields in Example 2 relative to thelarger-pore SAPO-5.

Small-pore SAPO-34 prepared in accordance with Example 9 and U.S. Pat.4,440,871 also was compared, using isobutane adsorption to characterizepore size to SAPO-11, which represents a MP-NZMS of the presentinvention:

    ______________________________________                                        Isobutane   Pressure     Temp.,  Weight %                                     Adsorption  Torr         °C.,                                                                           Adsorbed                                     ______________________________________                                        SAPO-11     500          20      4.5                                          SAPO-34     500          20      0.7                                          ______________________________________                                    

Since SAPO-34 does not attain 2 wt. % isobutane adsorption, SAPO-34 isnot an NZMS of the present invention. As discussed in Example 9, SAPO-34demonstrates inferior yields relative to SAPO-11.

What is claimed is:
 1. A catalyst system comprising a physical mixtureof:(a) a primary reforming catalyst comprising an effective amount of aplatinum-group metal component supported on a refractory inorganicoxide; and, (b) a molecular-sieve reforming catalyst comprising amountseffective to render the catalyst active as a reforming catalyst of atleast one MP-NZMS characterized in the calcined form by an adsorption ofisobutane of at least 2 percent by weight at a partial pressure of 500torr and a temperature of 20° C. and also characterized by an adsorptionof triethylamine less than about 5 percent by weight at a partialpressure of 2.6 torr and a temperature of 22° C., an inorganic-oxidebinder and at least one Group VIII metal.
 2. The catalyst system ofclaim 1 wherein the adsorption of triethylamine of the MP-NZMS is lessthan about 3 percent by weight.
 3. The catalyst system of claim 1wherein the MP-NZMS is present in an amount of between about 1 and about99.9 weight percent based on the total catalyst weight.
 4. The catalystsystem of claim 1 wherein the refractory inorganic oxide of step (a)comprises an alumina.
 5. The process according to claim 1 wherein theplatinum-group metal component of step (a) is present in the primaryreforming catalyst on an elemental basis in an amount of between about0.1 and 2 wt. %, based on the total weight of the catalyst.
 6. Thecatalyst system of claim 1 wherein the primary reforming catalystfurther comprises from about 0.1 to 5 wt. % of a metal promoter selectedfrom the group consisting of one or more of rhenium, indium and GroupIVA metals.
 7. The catalyst system of claim 1 wherein the Group VIIImetal of step (b) is present in the molecular-sieve reforming catalyston an elemental basis in an amount of between about 0.1 and 2 wt. %,based on the total weight of the catalyst.
 8. The catalyst system ofclaim 1 wherein the MP-NZMS is one or more selected from the group ofsilicoaluminophosphate molecular sieves.
 9. The catalyst system of claim8 wherein the MP-NZMS is one or more from the group consisting ofSAPO-11, SAPO-31, SAPO-40 and SAPO-41.
 10. The catalyst system of claim9 wherein the MP-NZMS consists essentially of SAPO-11.
 11. The catalystsystem of claim 1 wherein the physical mixture of the primary and themolecular-sieve reforming catalysts is contained on the same catalystparticle.